Construction of C–N bonds from small-molecule precursors through heterogeneous electrocatalysis

Li, Junnan; Zhang, Yuxuan; Kuruvinashetti, Kiran; Kornienko, Nikolay

doi:10.1038/s41570-022-00379-5

Cited by 182 publications

(129 citation statements)

References 143 publications

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“…The electrosynthesis of urea has been proposed as a simple and onsite production method. We strongly advise the readers to read Kornienko's review on C-N construction by electrocatalysis [460] and Wang's review on C-N coupling for urea electrosynthesis [461]. Wang et al recently reported a breakthrough strategy for fixing N2/CO2 simultaneously for mild urea generation by electrocatalytically coupling two gaseous molecules, namely, N2 and CO2, into urea [462].…”

Section: C-n Coupling Reaction To Amide Urea and Amine (Methylamine)mentioning

confidence: 99%

Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Sun

Liang

Liu

et al. 2022

Nano Research Energy

333

229

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To restore the natural nitrogen cycle (N-cycle), artificial N-cycle electrocatalysis with flexibility, sustainability, and compatibility can convert intermittent renewable energy (e.g., wind) to harmful or value-added chemicals with minimal carbon emissions. The background of such N-cycles, such as nitrogen fixation, ammonia oxidation, and nitrate reduction, is briefly introduced here. The discussion of emerging nanostructures in various conversion reactions is focused on the architecture/compositional design, electrochemical performances, reaction mechanisms, and instructive tests. Energy device advancements for achieving more functions as well as in situ/operando characterizations toward understanding key steps are also highlighted. Furthermore, some recently proposed reactions as well as less discussed C-N coupling reactions are also summarized. We classify inorganic nitrogen sources that convert to each other under an applied voltage into three types, namely, abundant nitrogen, toxic nitrate (nitrite), and nitrogen oxides, and useful compounds such as ammonia, hydrazine, and hydroxylamine, with the goal of providing more critical insights into strategies to facilitate the development of our circular nitrogen economy.

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Section: C-n Coupling Reaction To Amide Urea and Amine (Methylamine)mentioning

confidence: 99%

Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Sun

Liang

Liu

et al. 2022

Nano Research Energy

333

229

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“…CO2, N2, H2O…) (4) and this includes directions such as H2O2 electrosynthesis from water and O2,(5) N2 reduction for NH3 production, (6) and the formation of products with C-N bonds. (7) Despite sulfur's abundance on earth and the importance of molecules with C-S bonds in biology, (8,9) pharma, (10) agriculture, (11) battery technologies (12) and optoelectronic materials,(13) (Fig. 1a) the electrosynthesis of such species remains unexplored.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Formation C-S Bonds from CO2 and Small Molecule Sulfur Species

Kornienko

Al‐Mahayni

et al. 2022

Preprint

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The formation of C-S bonds is an important step in the synthesis of pharmaceutical, biological, and chemical products. A very attractive green route to C-S bond containing species would be one driven through electrocatalysis using abundant small molecule precursors but examples within this context are largely absent from the literature. To this end, this work demonstrates the use of CO2 and SO32- as cheap building blocks that couple on the surface Cu-based heterogeneous catalysts to form hydroxymethanesulfonate, sulfoacetate and methane sulfonate for the first time, with Faradaic efficiencies of up to 9.5%. A combination of operando measurements and computational modelling reveal that *CHOH formed on metallic Cu is a key electrophilic intermediate that is nucleophilically attacked by SO32- in the principal C-S bond forming step. In all, the proof-of-concept for electrocatalytic C-S bond formation and mechanistic insights gained stand to substantially broaden the scope of the emerging field of electrosynthesis.

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“…A major reason preventing the C–N bond formation is the repulsive dipole–dipole interaction between the adjacent precursor molecules. , Previous studies have shown that the interaction between the catalytic sites and the adsorbents determines whether the adsorbents couple with each other to form organonitrogens or are reduced without coupling. , Although both carbonaceous and nitrogenous intermediates (e.g., *CO and *NO) are activated through the electron “donor–acceptor” interaction with the catalytic sites, they both concurrently possess the occupied σ orbitals . Consequently, the C–N coupling between them is electrostatically hindered by the dipole–dipole repulsion .…”

mentioning

confidence: 99%

“…Although both carbonaceous and nitrogenous intermediates (e.g., *CO and *NO) are activated through the electron "donor−acceptor" interaction with the catalytic sites, 12 they both concurrently possess the occupied σ orbitals. 11 Consequently, the C−N coupling between them is electrostatically hindered by the dipole−dipole repulsion. 13 In addition, for a facile C−N coupling, the hybridization between the 2p orbital of a N/C atom in the adsorbed intermediate and the 3d orbital of the metal sites should be moderate.…”

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confidence: 99%

Carbene Ligands Enabled C–N Coupling for Methylamine Electrosynthesis: A Computational Study

et al. 2022

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Electrocatalytic conversion of carbon monoxide (CO) and nitric oxide (NO) into methylamine (MMA, CH3NH2) could convert excessive renewable energy and environmental pollutants into valuable chemicals. The main hurdle, however, is the inefficient C–N coupling as a result of the repulsive dipole–dipole interaction between adjacent coupling precursors. Herein, we report a simple strategy to weaken the repulsive dipole–dipole interaction using N-heterocyclic carbene to modify the pristine catalyst surface. The pristine catalyst for our study is MXene-doped with two Cu atoms using the O vacancy site of Mo2NO2 (Cu2@v-Mo2NO2). Our molecular modeling work based on density functional theory calculation discovered that surface-functionalized carbene ligands perturb the electronic configuration of chelated Cu sites, hence causing charge redistribution on the adsorbed reaction intermediates. Such charge redistribution successfully weakens the CO/NO dipole–dipole repulsion, effectively optimizes the binding strength of precursors, and leads to an effective C–N bond formation. Consequently, a pathway that selectively converts CO and NO to MMA with a facile C–N coupling step and low limiting potential is identified on the catalyst surface. Our work suggests a facile electrocatalyst surface functionalization strategy for the improved coupling between small-molecule precursors featuring dipole–dipole repulsion, with the potential to generalize to the sustainable synthesis of multi-carbon/nitrogen chemicals.

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Construction of C–N bonds from small-molecule precursors through heterogeneous electrocatalysis

Cited by 182 publications

References 143 publications

Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Electrochemical Formation C-S Bonds from CO2 and Small Molecule Sulfur Species

Carbene Ligands Enabled C–N Coupling for Methylamine Electrosynthesis: A Computational Study

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