Electrocatalytic hydrogenation of quinolines with water over a fluorine-modified cobalt catalyst

Guo, Shuoshuo; Wu, Yongmeng; Wang, Changhong; Gao, Ying; Li, Mengyang; Zhang, Bin; Liu, Cuibo

doi:10.1038/s41467-022-32933-6

Cited by 38 publications

(20 citation statements)

References 65 publications

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“…Moreover, we further synthesized fluorine-modified low-coordinated metallic cobalt. By the synergism of surface fluorine and unsaturated sites to enhance the adsorption of quinoline (QN) while weakening the adsorption of hydrogenated 1,2,3,4-tetrahydroquinoline (THQ) on the Co surface, electrocatalytic QN-to-THQ with high activity and selectivity is realized …”

Section: Electrocatalytic Hydrogenation Of Organics With H2o Over Nan...mentioning

confidence: 99%

Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Liu

Zhao

et al. 2023

Acc. Chem. Res.

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Conspectus The hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic hydrogenation by using water (H2O) as the hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid the use of high-pressure and flammable hydrogen gas or other toxic/expensive hydrogen donors, which usually cause environmental, safety, and cost concerns. Interestingly, utilizing easily available heavy water (D2O) for deuterated syntheses is also attractive due to the widespread applications of deuterated molecules in organic synthesis and the pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, and how electrodes dictate reaction outcomes remains elusive. Therefore, the rational design of nanostructured electrodes for driving the electrocatalytic hydrogenation of a series of organics via H2O electrolysis is developed. In this Account, we review recent advances in the electrocatalytic hydrogenation of different types of organic functional groups, including CC, CN, CC, CO, and C–Br/I bonds, −NO2, and N-heterocycles, with H2O over nanostructured cathodes. First, the general reaction steps (reactant/intermediate adsorption, active atomic hydrogen (H*) formation, surface hydrogenation reaction, product desorption) are analyzed, and key factors are proposed to optimize hydrogenation performance (e.g., selectivity, activity, Faradaic efficiency (FE), reaction rate, and productivity) and inhibit side reactions. Then, ex situ and in situ spectroscopic tools to study key intermediates and interpret mechanisms are introduced. Third, based on the knowledge of key reaction steps and mechanisms, we introduce catalyst design principles in detail on how to optimize the adoption of reactants and key intermediates, promote the formation of H* from water electrolysis, inhibit hydrogen evolution and side reactions, and improve the selectivity, reaction rate, FEs, and space-time productivity of products. We then introduce some typical examples. (i) P- and S-modified Pd can decrease CC adsorption and promote H* formation, enabling semihydrogenation of alkynes with high selectivity and FEs at lower potentials. Then, creating high-curvature nanotips to concentrate the substrates further speeds up the hydrogenation process. (ii) By introducing low-coordination sites into Fe and combining low-coordination sites and surface fluorine to modify Co to optimize the adsorption of intermediates and facilitate H* formation, hydrogenation of nitriles and N-heterocycles with high activity and selectivity is obtained. (iii) By forming isolated Pd sites to induce a specific σ-alkynyl adsorption of alkynes and steering S vacancies of Co3S4–x to preferentially adsorb −NO2, hydrogenation of easily reduced group-decorated alkynes and nitroarenes with high chemoselectivity is realized. (iv) For gas reactant participated reactions, by designing hydrophobic gas diffusion...

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Section: Electrocatalytic Hydrogenation Of Organics With H2o Over Nan...mentioning

confidence: 99%

Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Liu

Zhao

et al. 2023

Acc. Chem. Res.

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“…3b). 26 Subsequently, the reaction solution was studied by electron paramagnetic resonance (EPR) measurements, 27 confirming the formation of H radicals from water (Fig. S30, ESI†).…”

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confidence: 92%

Ag/Ni–MOF heterostructure with synergistic enrichment and activation properties for electrocatalytic reduction of 4-nitrophenol

et al. 2022

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“…However, the source of gaseous hydrogen and the addition of toxic Pb limit the vigorous development of selective hydrogenation. Recently, electrochemical selective hydrogenation technology driven by renewable and clean energy displays substantial benefits, such as low energy consumption and environmental friendliness, which holds great promise for the selective hydrogenation. − Moreover, it can directly utilize water or protons generated at the cathode as the source of active H*, avoiding the use of hazardous hydrogen or deleterious organic solvents. − Since the electrochemical hydrogenation reaction is carried out under aqueous conditions, the water dissociation inevitably becomes a competitive reaction, eventually leading to poor Faradaic efficiencies (FEs) and conversions. , More importantly, the competitive relationship between electrochemical hydrogenation reaction and hydrogen evolution reaction (HER) remains elusive …”

Section: Introductionmentioning

confidence: 99%

Dopant- and Surfactant-Tuned Electrode–Electrolyte Interface Enabling Efficient Alkynol Semi-Hydrogenation

Zhao

Huang

et al. 2023

J. Am. Chem. Soc.

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Electrochemical alkynol semi-hydrogenation has emerged as a sustainable and environmentally benign route for the production of high-value alkenols, featuring water as the hydrogen source instead of H2. It is highly challenging to design the electrode–electrolyte interface with efficient electrocatalysts and their matched electrolytes to break the selectivity-activity stereotype. Here, boron-doped Pd catalysts (PdB) and surfactant-modified interface are proposed to enable the simultaneous increase in alkenol selectivity and alkynol conversion. Typically, compared to pure Pd and commercial Pd/C catalysts, the PdB catalyst achieves both higher turnover frequency (139.8 h–1) and specific selectivity (above 90%) for the semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY). Quaternary ammonium cationic surfactants that are employed as electrolyte additives are assembled at the electrified interface in response to applied bias potential, establishing an interfacial microenvironment that can facilitate alkynol transfer and hinder water transfer suitably. Eventually the hydrogen evolution reaction is inhibited and alkynol semi-hydrogenation is promoted, without inducing the decrease of alkenol selectivity. This work offers a distinct perspective on creating a suitable electrode–electrolyte interface for electrosynthesis.

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Electrocatalytic hydrogenation of quinolines with water over a fluorine-modified cobalt catalyst

Cited by 38 publications

References 65 publications

Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Ag/Ni–MOF heterostructure with synergistic enrichment and activation properties for electrocatalytic reduction of 4-nitrophenol

Dopant- and Surfactant-Tuned Electrode–Electrolyte Interface Enabling Efficient Alkynol Semi-Hydrogenation

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