“…27 – 29 and Supplementary Table 6 ). Obviously, the binding strength of Pd (111) and PdH x (111) is neither too strong nor too weak, which might be favorable for catalysis based on Sabatier principle 39 , 40 . Fig.…”
Electrochemical hydrogenation of acetonitrile based on well-developed proton exchange membrane electrolyzers holds great promise for practical production of ethylamine. However, the local acidic condition of proton exchange membrane results in severe competitive proton reduction reaction and poor selection toward acetonitrile hydrogenation. Herein, we conduct a systematic study to screen various metallic catalysts and discover Pd/C exhibits a 43.8% ethylamine Faradaic efficiency at the current density of 200 mA cm−2 with a specific production rate of 2912.5 mmol g−1 h−1, which is about an order of magnitude higher than the other screened metal catalysts. Operando characterizations indicate the in-situ formed PdHx is the active centers for catalytic reaction and the adsorption strength of the *MeCH2NH2 intermediate dictates the catalytic selectivity. More importantly, the theoretical analysis reveals a classic d-band mediated volcano curve to describe the relation between the electronic structures of catalysts and activity, which could provide valuable insights for designing more effective catalysts for electrochemical hydrogenation reactions and beyond.
“…27 – 29 and Supplementary Table 6 ). Obviously, the binding strength of Pd (111) and PdH x (111) is neither too strong nor too weak, which might be favorable for catalysis based on Sabatier principle 39 , 40 . Fig.…”
Electrochemical hydrogenation of acetonitrile based on well-developed proton exchange membrane electrolyzers holds great promise for practical production of ethylamine. However, the local acidic condition of proton exchange membrane results in severe competitive proton reduction reaction and poor selection toward acetonitrile hydrogenation. Herein, we conduct a systematic study to screen various metallic catalysts and discover Pd/C exhibits a 43.8% ethylamine Faradaic efficiency at the current density of 200 mA cm−2 with a specific production rate of 2912.5 mmol g−1 h−1, which is about an order of magnitude higher than the other screened metal catalysts. Operando characterizations indicate the in-situ formed PdHx is the active centers for catalytic reaction and the adsorption strength of the *MeCH2NH2 intermediate dictates the catalytic selectivity. More importantly, the theoretical analysis reveals a classic d-band mediated volcano curve to describe the relation between the electronic structures of catalysts and activity, which could provide valuable insights for designing more effective catalysts for electrochemical hydrogenation reactions and beyond.
“…Direct hydrogenation of acetonitrile (MeCN) to ethylamine (EtNH 2 ) is a feasible process that can thoroughly utilize the excess MeCN from acrylonitrile production 1–4 . EtNH 2 is a fundamental raw material and intermediate for pharmaceuticals, agrochemicals, dyestuffs, and other fine chemicals, 5,6 with a wide range of applications for hydrogen storage, energy conversion, and other fields 7–17 .…”
Electrochemical acetonitrile hydrogenation compared with thermocatalytic hydrogenation provides a potential route to produce ethylamine in mild conditions. It is challenging to suppress the C–C coupling for improving ethylamine selectivity. Here, Ru‐supported Cu nanowire catalysts (Ru‐Cu NWs) are designed to achieve nearly 100% specific selectivity of ethylamine without coupling byproducts. In situ vibrational spectroscopy and electron spin resonance results reveal that the Ru‐Cu NWs provide a high active adsorption hydrogen (H*) coverage at the electrified interface so that the imine intermediates are more readily hydrogenated to generate ethylamine, thus suppressing the C–C coupling. Density functional theory calculations disclose that the formation of H* occurs more readily over Ru‐Cu NWs than Cu NWs. Moreover, the presence of Ru changes the potential‐determining step and facilitates the entire hydrogenation process. The strategy and understanding established here can be extended to other electrocatalytic hydrogenation reactions.
“…Ethylamine and acetonitrile are essential chemicals used in the production of fine chemicals. [28,40,41] However, the current industrial process for converting between ethylamine and acetonitrile is environmentally unfriendly, with high energy consumption and significant pollution. The conversion involves breaking and coupling of the CN triple bond, dehydrogenation and hydrogenation, and protection of the CC single bond, making it challenging to achieve electro-chemical reversible conversion between ethylamine and acetonitrile with high activity and selectivity.…”
Section: Introductionmentioning
confidence: 99%
“…Heterostructures have been shown to exhibit tremendous potential in catalysis due to their synergistic effect and abundant active sites at the interfaces. [5,[27][28][29][30][31][32] For example, heterostructured Ni/Ni(OH) 2 nanosheets, prepared using an in situ reduction strategy, exhibit better multifunctional electrocatalytic activity than their single counterparts for water splitting. [27] In situ introducing SnOx can efficiently enhance the catalytic activity and selectivity of metallic Pd nanosheets towards the selective CO 2 reduction.…”
Rational design of electrocatalysts is essential to achieve desirable performance of electrochemical synthesis process. Heterostructured catalysts have thus attracted widespread attention due to their multifunctional intrinsic properties, and diverse catalytic applications with corresponding outstanding activities. Here, we report an in‐situ restoration strategy for the synthesis of ultrathin Pd‐Ni(OH)2 nanosheets. Such Pd‐Ni(OH)2 nanosheets exhibit excellent activity and selectivity towards reversible electrochemical reforming of ethylamine and acetonitrile. In the acetonitrile reduction process, Pd acts as reaction center, while Ni(OH)2 provide proton hydrogen through promoting the dissociation of water. Also ethylamine oxidation process can be achieved on the surface of the heterostructured nanosheets with abundant Ni(II) defects. More importantly, an electrolytic cell driven by solar cells was successfully constructed to realize ethylamine‐acetonitrile reversible reforming. This work demonstrates the importance of heterostructure engineering in the rational synthesis of multifunctional catalysts towards electrochemical synthesis of fine chemicals.
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