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

Abstract

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.

Modulating the d-Band Center of Palladium via Ethylene Glycol Modification: Accelerating Had Desorption for Enhanced Formate Electrooxidation

“…Specifically, the peaks at 23.15° (001), 24.55° (200), 33.69° (201), and 34.81° (220) are attributed to WO 3 [Powder Diffraction File (PDF) number 20-1324] . Moreover, the peak at 40.44° (111) corresponds to metallic Pd(0), as per PDF number 46-1043 . These XRD findings align well with the previously discussed HRTEM results, confirming the crystalline nature of the catalysts.…”

Electrocatalytic Hydrogenation Using Palladium Membrane Reactors

“…This modification emphasized the crucial role of enhanced hydrogen atomic sieving in increasing the overall catalytic efficiency. 44 The promising results obtained in alkene hydrogenation using ePMRs led the Berlinguette group to undertake a systematic comparison between ePMR and conventional ECH reactors. 45 This study aimed to assess their performance in hydrogenating alkenes and alkynes under ambient conditions.…”

“…Su et al further optimized the system by fabricating a vertically aligned, tree-like array of Pd nanodendrites on the Pd membrane, which led to an appreciable increase in butadiene conversion. This modification emphasized the crucial role of enhanced hydrogen atomic sieving in increasing the overall catalytic efficiency …”

“…This modification emphasized the crucial role of enhanced hydrogen atomic sieving in increasing the overall catalytic efficiency. 44 …”

“…Compared to traditional thermocatalytic hydrogenation, electrocatalytic hydrogenation offers several advantages due to its elimination of the need for H 2 . − First, it circumvents the kinetic barrier associated with the thermal splitting of H 2 , allowing for reactions to occur under ambient conditions. Second, the issues related to the low solubility and mass transport of H 2 in reaction solutions are also avoided, as water can commonly serve as the hydrogen source.…”