Vacancy‐Rich Ni(OH)₂ Drives the Electrooxidation of Amino C−N Bonds to Nitrile C≡N Bonds

Abstract

Electrochemical synthesis based on electrons as reagents provides a broad prospect for commodity chemical manufacturing. A direct one‐step route for the electrooxidation of amino C−N bonds to nitrile C≡N bonds offers an alternative pathway for nitrile production. However, this route has not been fully explored with respect to either the chemical bond reforming process or the performance optimization. Proposed here is a model of vacancy‐rich Ni(OH)2 atomic layers for studying the performance relationship with respect to structure. Theoretical calculations show the vacancy‐induced local electropositive sites chemisorb the N atom with a lone pair of electrons and then attack the corresponding N(sp3)−H, thus accelerating amino C−N bond activation for dehydrogenation directly into the C≡N bond. Vacancy‐rich nanosheets exhibit up to 96.5 % propionitrile selectivity at a moderate potential of 1.38 V. These findings can lead to a new pathway for facilitating catalytic reactions in the chemicals industry.

Active/Conductive Layer Stacked Superlattices for Highly Selective CO2 Electroreduction

“…Along the way, substantial efforts have been devoted to exploring the e cient catalysts derived from these metal oxides 17,18,19,20,21,22 . However, with this selfreduction, the competitive hydrogen evolution reaction (HER) performance of the derived metal catalysts will gradually dominate 1,16,22,23,24,25,26 , resulting in their CO 2 RR activity are di cult to maintain in a wide potential window. Actually, this spontaneous self-reduction of metal oxides is contradictory to the high selective CO 2 RR performance.…”

Divergent Paths, Same Goal: A Pair‐Electrosynthesis Tactic for Cost‐Efficient and Exclusive Formate Production by Metal–Organic‐Framework‐Derived 2D Electrocatalysts

“…These results demonstrate the structural transformation of Ni‐MOFs to Ni(OH) 2 under the electrochemical conditions. [ 39,44 ] Therefore, for comparison, Ni(OH) 2 ‐NF was also directly prepared as a control sample. In Ni(OH) 2 ‐NF, SEM and TEM images show that Ni(OH) 2 features an intriguing nanowire‐terminated nanosheet morphology and was uniformly grown on the NF surface (Figure S9, Supporting Information).…”

“…[ 33,34 ] Unlike high‐temperature pyrolysis, [ 35–37 ] in situ electrochemical treatment of MOFs represents a newly emerging strategy to develop advanced electrocatalysts with the rational design of the MOF precursors. [ 38–41 ] Herein, a pair‐electrosynthesis tactic integrating MOR and CO 2 RR for concurrent formate production in both electrodes has been conceptually developed, in which the self‐supported Ni‐MOF‐derived nanosheet arrays (Ni‐NF‐Af) and a series of Bi‐MOF‐derived Bi‐enes were designed and prepared through an in situ electrochemical conversion process as efficient anodic and cathodic electrocatalysts, respectively. The as‐prepared Ni‐NF‐Af used as the MOR electrocatalyst only needs low potentials of 1.345 and 1.388 V to reach the large current densities of 100 and 500 mA cm −2 for methanol‐to‐formate conversion with ≈100% selectivity, much superior over most of the reported Ni‐based electrocatalysts.…”

Design of NiOx/Carbon Heterostructure Interlayer to Improve Hole Extraction Efficiency of Inverted Perovskite Solar Cells

“…In Figure 2c, we can also clearly observe the larger area of the peak at 531.2 eV for NiO x shell of NCHs, suggesting the existence of abundant O vacancies. [40,41] These may synergistically contribute to the better conductivity and hole mobility for NCHs. [28,42] In order to confirm these, the space charge limited current (SCLC) method was adopted to measure hole mobility by constructing hole-only devices (Figure S3, Supporting Information).…”