Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation: propene on palladium

Winiwarter, Anna; Silvioli, Luca; Scott, Søren B.; Enemark‐Rasmussen, Kasper; Šarić, Manuel; Trimarco, Daniel Bøndergaard; Vesborg, Peter Christian Kjærgaard; Moses, Poul Georg; Stephens, Ifan E. L.; Seger, Brian; Chorkendorff, Ib

doi:10.1039/c8ee03426e

Cited by 65 publications

(119 citation statements)

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“…CVs performed after CO and propene adsorption show suppression of H upd features in the potential region of 0.0–0.4 V vs. RHE, due to poisoning from adsorbed species, consistent with expectations [21–23] . The oxidation features observed for CO stripping and propene stripping are also consistent with those described previously under similar conditions [2,23] . We see that CO is anodically stripped with a sharp oxidative peak observed at ca.…”

Section: Resultssupporting

confidence: 90%

“…Comparing the adsorption energy of a selection of propene‐derived intermediates and CO calculated using Density Functional Theory (DFT) [2,24] (see Figure S14), it becomes clear that some propene‐derived species adsorb more strongly than CO, particularly at potentials above 0.4 V vs. RHE, which is in agreement with the experimental observations of displacement.…”

Section: Resultssupporting

confidence: 74%

“…In our previous study [2] we reported that propene adsorbed on a palladium surface can be partially removed at potentials lower than 0.4 V vs. RHE both directly as propene (C 3 H 6 ) and as the hydrogenation product propane (C 3 H 8 ). Other forms of adsorbed propene are more strongly bound and can only be removed at potentials higher than 1.0 V vs. RHE in form of CO 2 .…”

Section: Resultsmentioning

confidence: 99%

“…DFT calculations for electrochemical propene oxidation suggest that the in‐situ formed spectator species are predominantly C x H y species [2] . Experimental probes are also important to ascertain the nature of the adsorbed species.…”

Section: Methodsmentioning

confidence: 99%

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CO as a Probe Molecule to Study Surface Adsorbates during Electrochemical Oxidation of Propene

et al. 2021

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A major challenge in the electrochemical oxidation of hydrocarbons is understanding the formation of intermediate species, some of which continue to react, while others are non‐reactive or poisonous species that block adsorption of further reactants. Herein we investigate the identity and behavior of adsorbates formed during partial oxidation of propene. We employ two techniques: Electrochemistry‐Mass Spectrometry (EC‐MS) and Attenuated Total Reflection Infrared Spectroscopy (ATR‐FTIR). In both cases, we use CO as a probe molecule, to perturb the ad‐layer of propene intermediates. In the EC‐MS experiments, propene and its intermediates were quantified by triggering their desorption via displacement with CO. We show evidence for at least two distinct classes of propene adsorbates, via CO displacement and electrochemical stripping. A redshift in the ν(C−O) mode was observed, during IR spectroscopy, reflecting the chemical environment arising from strongly bound propene intermediates.

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 74%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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CO as a Probe Molecule to Study Surface Adsorbates during Electrochemical Oxidation of Propene

et al. 2021

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“…The palladium is still frequently employed as anodic electrode for the activation of small organic molecules in PEMFC . Winiwarter et al . showed that Pd could be promising for the application in this reactor type, because for this metal (M) there is formation of a thin layer of PdO (M−O) on electrocatalyst surface, where the oxide can activate the C−H bond in methane and the water molecule; it is also utilized for hydrocarbon oxidation, due to its carbophilic properties.…”

Section: Figurementioning

confidence: 99%

Obtaining C₂ and C₃ Products from Methane Using Pd/C as Anode in a Solid Fuel Cell‐type Electrolyte Reactor

et al. 2020

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Methane was converted into C2 and C3 products under mild conditions using a single stage solid electrolyte reactor, using a proton exchange membrane fuel cell as a SER-FC and Pd/C as an electrocatalyst prepared by the reduction method of sodium borohydride. This electrocatalyst has a cubic pattern of palladium centered on the face and an average size of nanoparticles close to 6.4 nm, according to the literature. Differential mass spectrometry reveals the chemical profile of species obtained from the oxidation of methane with ionic currents (Ii) at m/z = 16, 28, 30, 32, 44, 46 and 60. In many cases, Ii can be assigned to more than one species; therefore, complementary ATR-FTIR experiments were performed. The ATR-FTIR spectra confirmed the presence of C2 and C3 compounds such as ethane, ethanol, acetaldehyde, acetic acid and propane. Considering the low amount of water in the reaction medium, these results may be associated with the use of Pd/C electrocatalysts responsible for the activation of the water molecule. The availability of natural gas currently rivals with oil; however, this hydrocarbon is not as versatile as crude oil. [1] The main component of natural gas is methane, the most stable hydrocarbon, with the very high dissociation energy of CÀ H bond (435 kJ mol À 1). [2] Its tetrahedral structure is difficult to polarize; therefore, it makes this molecule almost inert to mild conditions. [3] Turning this gas into higher value-added products is a great goal. Current approaches to utilization of methane involve mainly high-temperature processes to produce syngas (H 2 + CO), which further can be transformed into methanol or fuels. [2] The ethane is a vital building block in the chemical industry with an expectedly of increasing demand in obtaining C2 or longer compounds. [4] The oxidative coupling of methane (OCM) is a direct and exothermic process and not limited by any thermodynamic constraints. [1a]

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Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

Zheng,

Zhang,

Wang

et al. 2024

Advanced Materials

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Hydrogenation reactions play a critical role in the synthesis of value‐added products within the chemical industry. Electrocatalytic hydrogenation (ECH) using water as the hydrogen source has emerged as an alternative to conventional thermocatalytic processes for sustainable and decentralized chemical synthesis under mild conditions. Among various ECH catalysts, copper‐based (Cu‐based) nanomaterials are promising candidates due to their earth‐abundance, unique electronic structure, versatility, and high activity/selectivity. Herein, recent advances in the application of Cu‐based catalysts in ECH reactions for the upgrading of valuable chemicals are systematically analyzed. The unique properties of Cu‐based catalysts in ECH are initially introduced, followed by the design strategies to enhance their activity and selectivity. Then, typical ECH reactions on Cu‐based catalysts are presented in detail, including carbon dioxide reduction for multicarbon generation, alkyne‐to‐alkene conversion, selective aldehyde conversion, ammonia production from nitrogen‐containing substances, and amine production from organic nitrogen compounds. In these catalysts, we focus on the role of catalyst composition and nanostructures toward different products. The co‐hydrogenation of two substrates (e.g., CO2 and NOxn, CO2 and SO32–, etc.) via C–N, C–S, and C–C cross‐coupling reactions are also highlighted. Finally, the critical issues and future perspectives of Cu‐catalyzed ECH are proposed to accelerate the rational development of next‐generation catalysts.This article is protected by copyright. All rights reserved

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Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation: propene on palladium

Abstract: High coverage of the catalyst surface generated by in situ degradation of propene steers the reaction towards allylic oxidation.

Cited by 65 publications

References 48 publications

CO as a Probe Molecule to Study Surface Adsorbates during Electrochemical Oxidation of Propene

CO as a Probe Molecule to Study Surface Adsorbates during Electrochemical Oxidation of Propene

Obtaining C₂ and C₃ Products from Methane Using Pd/C as Anode in a Solid Fuel Cell‐type Electrolyte Reactor

Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

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Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation: propene on palladium

Abstract: High coverage of the catalyst surface generated by in situ degradation of propene steers the reaction towards allylic oxidation.

Cited by 65 publications

References 48 publications

CO as a Probe Molecule to Study Surface Adsorbates during Electrochemical Oxidation of Propene

CO as a Probe Molecule to Study Surface Adsorbates during Electrochemical Oxidation of Propene

Obtaining C2 and C3 Products from Methane Using Pd/C as Anode in a Solid Fuel Cell‐type Electrolyte Reactor

Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

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Obtaining C₂ and C₃ Products from Methane Using Pd/C as Anode in a Solid Fuel Cell‐type Electrolyte Reactor