Electro-oxidation of propylene by palladium functionalized titanium hollow fibre electrodes

Jong, Ronald P.H.; Dubbelman, E.; Mul, Guido

doi:10.1016/j.jcat.2022.10.007

Cited by 10 publications

(5 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Acetone has previously been reported to be a major product of homogeneous reactions involving Pd 2+ in solution. , We checked our electrolyte and found increased Pd 2+ concentration, presumably from the dissolution of the electrocatalyst in time (Figure S5).…”

Section: Resultsmentioning

confidence: 99%

“…Earlier studies on propylene oxidation in acidic media reported the oxidation of allylic carbon at a low overpotential and investigated propylene adsorption; unfortunately, these efforts, carried out on Pd, ,, led to a broad suite of partially oxidized products that include allyl alcohol, acrolein, and acrylic acid. Propylene glycol formation was also studied at a high potential under which PdO is formed, ,− but here, the FE for PG was lower than 40%, and Pd 2+ dissolution led to acetone formation. The functionalization of the C  C double bond has been found to be more selective on Ag-based catalysts at higher overpotentials, but here, the faradic efficiency (FE) has been limited to 20% .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Selective Electrified Propylene-to-Propylene Glycol Oxidation on Activated Rh-Doped Pd

Huang,

Chen,

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Renewable-energy-powered electrosynthesis has the potential to contribute to decarbonizing the production of propylene glycol, a chemical that is used currently in the manufacture of polyesters and antifreeze and has a high carbon intensity. Unfortunately, to date, the electrooxidation of propylene under ambient conditions has suffered from a wide product distribution, leading to a low faradic efficiency toward the desired propylene glycol. We undertook mechanistic investigations and found that the reconstruction of Pd to PdO occurs, followed by hydroxide formation under anodic bias. The formation of this metastable hydroxide layer arrests the progressive dissolution of Pd in a locally acidic environment, increases the activity, and steers the reaction pathway toward propylene glycol. Rh-doped Pd further improves propylene glycol selectivity. Density functional theory (DFT) suggests that the Rh dopant lowers the energy associated with the production of the final intermediate in propylene glycol formation and renders the desorption step spontaneous, a concept consistent with experimental studies. We report a 75% faradic efficiency toward propylene glycol maintained over 100 h of operation.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Selective Electrified Propylene-to-Propylene Glycol Oxidation on Activated Rh-Doped Pd

Huang,

Chen,

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Previously studied catalysts for electrochemical propylene epoxidation can be clustered into palladium-derived (Pd) (9)(10)(11)(12), platinumderived (Pt) (13)(14)(15), and silver-derived (Ag) (16,17) groups (Fig. 1B and table S1), and the best catalytic performance for electrochemical epoxidation has been observed with oxidized Pd and Pt catalysts.…”

Section: Catalytic Performance Of Pdpto X /C and Design Principlementioning

confidence: 99%

Direct propylene epoxidation via water activation over Pd-Pt electrocatalysts

Chung,

Maalouf,

Adams

et al. 2024

Science

View full text Add to dashboard Cite

Direct electrochemical propylene epoxidation by means of water-oxidation intermediates presents a sustainable alternative to existing routes that involve hazardous chlorine or peroxide reagents. We report an oxidized palladium-platinum alloy catalyst (PdPtO x /C), which reaches a Faradaic efficiency of 66 ± 5% toward propylene epoxidation at 50 milliamperes per square centimeter at ambient temperature and pressure. Embedding platinum into the palladium oxide crystal structure stabilized oxidized platinum species, resulting in improved catalyst performance. The reaction kinetics suggest that epoxidation on PdPtO x /C proceeds through electrophilic attack by metal-bound peroxo intermediates. This work demonstrates an effective strategy for selective electrochemical oxygen-atom transfer from water, without mediators, for diverse oxygenation reactions.

show abstract

“…Studies on electrochemical propylene epoxidation have been conducted previously using Pd-derived, Pt-derived and Ag-derived catalysts. 16,[28][29][30][31] The Pd catalysts facilitated epoxidation on the surface oxide layer at anodic potentials larger than 1.1 V vs. RHE. The performance of the oxidized Pt catalyst was found to correlate with an increase of Pt(II) and Pt(IV) species on the surface, whereas pure PtO 2 was less active.…”

Section: Zhiyong Tangmentioning

confidence: 99%