Theoretical investigation of selective hydrogenation of 1,3-butadiene on Pt doping Cu nanoparticles

Liu, Da‐Yan; Chen, H.Y.; Zhang, J.Y.; Huang, Jianyu; Li, Y.M.; Peng, Qiuming

doi:10.1016/j.apsusc.2018.06.123

Cited by 14 publications

(5 citation statements)

References 38 publications

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“…Moreover, the low energy barriers (< 0.8 eV) indicates that the diffusion processes are spontaneous. [19] DFT calculation in Figure S13 predicts that, with a slow H a generation, H a prefers to penetrate into Pd-based membrane owing to the lower energy barrier of H a penetration than that of H a combination to H 2 (Ea 3 � 1.09 eV in Table S3). Therefore, accelerating H a consumption could bring a rapid H a atomic sieving under the slow H a formation (e.g., high TOF and FE for Type D in Figure 2f).…”

Section: Methodsmentioning

confidence: 99%

H₂‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array

et al. 2023

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H2‐free semi‐hydrogenation at room temperature shows great advantage for replacing the thermocatalytic process in industry owing to the high energy and resource saving, however, remains great challenges. Herein, a tree‐like Pd dendrites array decorated Pd membrane was constructed as the core device in an electrochemistry assisted gas‐fed membrane reactor for butadiene semi‐hydrogenation. It reveals that hydrogen atomic sieving effect of this Pd‐based membrane under electrochemical condition was the key for semi‐hydrogenation. The configuration study of Pd nanostructured membrane demonstrates that the penetration of hydrogen atoms through Pd membrane from electrochemical side to chemical side is affected by the consumption of hydrogen atom in semi‐hydrogenation step. Such atomic sieving property of nanostructured Pd membrane with 5.1 times increase in catalytic active surface area brings above 14 times higher in butadiene conversion than that of bare Pd foil, with ~90% of butenes selectivity at butadiene conversion ~98% over 300h of H2‐free reaction under 15 mA cm‐2.

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Section: Methodsmentioning

confidence: 99%

H₂‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array

et al. 2023

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“…Carbon monoxide is a reactant in many major catalytic processes and a common prototypical adsorbate, and copper catalysts are used for the hydrogenation of CO to methanol − and the low-temperature promotion of the water-shift reaction, − among other processes. When a second transition metal is added in small amounts, to form so-called single-atom alloys (SAA), copper can also be used as a selective catalyst for other reactions, for the hydrogenation of organic reactants with multiple double or triple bonds, for instance. − This latter application has been the motivation behind this study. , …”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of Carbon Monoxide Adsorption on Cu/SBA-15 Catalysts: Under Vacuum versus under Atmospheric Pressures

et al. 2022

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The thermodynamics of the adsorption of carbon monoxide on a copper-based catalyst were estimated by using data from in situ infrared absorption spectroscopy experiments. A direct comparison was performed between the energetics under a vacuum environment versus in the presence of CO gas. It was found that the magnitude of the enthalpy of adsorption is reduced by almost a factor of 4 in going from the first case to the second, from ΔH°ads,vacuum = −82 kJ/mol to ΔH°ads,CO‑atm = −21 kJ/mol. Furthermore, isosteric analysis of the data indicated that the magnitude of the latter decreases in the low-coverage limit, to values below ΔH°ads,CO‑atm = −18 kJ/mol, a trend opposite to what has been reported in other systems. These observations are explained in terms of the associated standard entropy of adsorption, which in the presence of gas-phase CO was estimated at ΔS°ads,CO‑atm ∼ −24 J/(mol K), a value much smaller in magnitude than the standard entropy of CO condensation. The excess entropy of CO adsorption over that of CO condensation is here ascribed to excess entropy in the adsorbed state due to additional phenomena induced by the gas-phase molecules such as adsorbate displacement and adsorbate-assisted adsorption steps.

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“…In alkyne hydrogenation excellent selectivity of SAAs toward alkene formation was reported for PdZn, PdCu, PdAu and PdAg compositions [14,[18][19][20][21][22][23]. The efficiency of PtCu in hydrogenation of 1,3-butadiene was discovered by Sykes et al [16,24] and theoretically confirmed by DFT calculations [25][26][27]. PtCu SAA catalyst exhibited high selectivity, stability and resistance to poisoning in hydrogenation of butadiene to butenes under industrial conditions.…”

Section: Introductionmentioning

confidence: 78%

Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd1Ag3/Al2O3 Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism

et al. 2021

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This research was focused on studying the performance of the Pd1Ag3/Al2O3 single-atom alloy (SAA) in the liquid-phase hydrogenation of di-substituted alkyne (1-phenyl-1-propyne), and development of a kinetic model adequately describing the reaction kinetic being also consistent with the reaction mechanism suggested for alkyne hydrogenation on SAA catalysts. Formation of the SAA structure on the surface of PdAg3 nanoparticles was confirmed by DRIFTS-CO, revealing the presence of single-atom Pd1 sites surrounded by Ag atoms (characteristic symmetrical band at 2046 cm−1) and almost complete absence of multiatomic Pdn surface sites (<0.2%). The catalyst demonstrated excellent selectivity in alkyne formation (95–97%), which is essentially independent of P(H2) and alkyne concentration. It is remarkable that selectivity remains almost constant upon variation of 1-phenyl-1-propyne (1-Ph-1-Pr) conversion from 5 to 95–98%, which indicates that a direct alkyne to alkane hydrogenation is negligible over Pd1Ag3 catalyst. The kinetics of 1-phenyl-1-propyne hydrogenation on Pd1Ag3/Al2O3 was adequately described by the Langmuir-Hinshelwood type of model developed on the basis of the reaction mechanism, which suggests competitive H2 and alkyne/alkene adsorption on single atom Pd1 centers surrounded by inactive Ag atoms. The model is capable to describe kinetic characteristics of 1-phenyl-1-propyne hydrogenation on SAA Pd1Ag3/Al2O3 catalyst with the excellent explanation degree (98.9%).

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Theoretical investigation of selective hydrogenation of 1,3-butadiene on Pt doping Cu nanoparticles

Cited by 14 publications

References 38 publications

H₂‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array

H₂‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array

Thermodynamics of Carbon Monoxide Adsorption on Cu/SBA-15 Catalysts: Under Vacuum versus under Atmospheric Pressures

Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd1Ag3/Al2O3 Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism

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Theoretical investigation of selective hydrogenation of 1,3-butadiene on Pt doping Cu nanoparticles

Cited by 14 publications

References 38 publications

H2‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array

H2‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array

Thermodynamics of Carbon Monoxide Adsorption on Cu/SBA-15 Catalysts: Under Vacuum versus under Atmospheric Pressures

Liquid-Phase Hydrogenation of 1-Phenyl-1-propyne on the Pd1Ag3/Al2O3 Single-Atom Alloy Catalyst: Kinetic Modeling and the Reaction Mechanism

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H₂‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array

H₂‐free Semi‐hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree‐like Pd Dendrites Array