Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode

Abstract

For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value-added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (-CH -NH ) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that Ni /Ni may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram-scale synthesis.

NiFe Oxalate Nanomesh Array with Homogenous Doping of Fe for Electrocatalytic Water Oxidation

“…Electrochemical water splitting is considered as a promising strategy for converting clean electricity into chemical energy . Water oxidation, one of the half reactions of water splitting, is the pivotal process because of its unfavorable thermodynamics and sluggish kinetics . Thus, the design of efficient, stable, and cheap oxygen evolution reaction (OER) electrocatalyst is an ongoing challenge.…”

Recent Advances in Electrochemical Hydrogen Production from Water Assisted by Alternative Oxidation Reactions

“…In a recent example, Zhang's group employed CoP and NiSe as the cathode and anode, respectively, and constructed a hybrid electrocatalysis system for boosting H 2 production via anodic oxidation of primary amines. [75] NiSe nanorod (~15 nm in diameter) arrays growth on Ni foam (Figure 6a-d) were prepared by direct selenization of commercially available Ni foam under hydrothermal conditions. Figure 6e showed the LSV curves recorded in 1.0 M KOH over the NiSe electrode in the presence and absence of benzylamine (chosen as the model primary amine substrate), respectively.…”

Lewis acid promoted dehydration of amides to nitriles catalyzed by [PSiP]‐pincer iron hydrides

“…Complexes 1-3 were prepared according to the literature procedures. [29,30] (9), Si1-Fe1-H1 92.40 (9) well as elemental analysis. In the IR spectrum of 4, a typical ν (Fe-H) stretching band was found at 1839 cm −1 .…”

“…It was also found that primary amides could transfer to the related nitriles by ZnCl 2 in CH 3 CN/H 2 O medium under microwave irradiation. [27] After we have studied the dehydration of amides to nitriles with hydrido iron or cobalt complexes as catalysts, [7][8][9][10][11][12][13][14][15][16][17][18]28] now we want to know if Lewis acids can promote these catalytic systems. Therefore, in order to expand the scope of the application of these hydrido iron complexes, four [PSiP]-pincer iron hydrides 1-4 were synthesized ( Figure 1) and their catalytic activities for dehydration of amides to nitriles were explored.…”