Nitrogenous Intermediates in NO<sub>x</sub>‐involved Electrocatalytic Reactions

Jia, Shunhan; Wu, Limin; Liu, Hanle; Wang, Ruhan; Sun, Xiaofu; Han, Buxing

doi:10.1002/anie.202400033

Angew Chem Int Ed

2024

DOI: 10.1002/anie.202400033

|View full text |Cite

Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions

Shunhan Jia,

Limin Wu,

Hanle Liu

et al.

Abstract: Chemical manufacturing utilizing renewable sources and energy emerges as a promising path towards sustainability and carbon neutrality. The electrocatalytic reactions involving nitrogen oxides (NOx) offered a potential strategy for synthesizing various nitrogenous chemicals. However, it is currently hindered by low selectivity/efficiency and limited reaction pathways, mainly due to the difficulties in controllable generation and utilization of nitrogenous intermediates. In this minireview, focusing on nitrogen… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2024

Publication Types

Select...

Article5

Relationship

Self Cite0

Independent5

Authors

Journals

Cited by 16 publications

References 69 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Ru‐Incorporation‐Induced Phase Transition in Co Nanoparticles for Low‐Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential

Wang,

Fan,

Luan

et al. 2024

Advanced Materials

View full text Add to dashboard Cite

Electrocatalytic reduction of nitric oxide (NO) to ammonia (NH3) represents a potential solution for improving the disrupted nitrogen cycle balance. Unfortunately, designing efficient electrocatalysts for NO reduction reaction (NORR) remains a notable challenge, especially at low concentrations. Herein, a displacement‐alloying strategy is reported to successfully induce the phase transition of Co nanoparticles supported on carbon nanosheets from face‐centered cubic (fcc) to hexagonal close‐packed (hcp) structure through Ru incorporation. The obtained RuCo alloy with hcp phase structure (hcp‐RuCo) exhibits apparent NORR activity with a record‐high Faraday efficiency of 99.2% and an NH3 yield of 77.76 µg h−1 mgcat−1 at −0.1 V versus reversible hydrogen electrode at a NO concentration of 1 vol %, surpassing Co nanoparticles with fcc phase structure and most reported catalysts. Density functional theory calculations reveal that the excellent NORR activity of hcp‐RuCo can be attributed to the optimized electronic structure of Co site and lowered energy barrier of the potential rate‐determining step through phase transition. Furthermore, the assembled Zn‐NO battery using hcp‐RuCo as the cathode achieves a power density of 2.33 mW cm−2 and an NH3 yield of 45.94 µg h−1 mgcat−1. This work provides a promising research perspective for low‐concentration NO conversion.

show abstract

Ru‐Incorporation‐Induced Phase Transition in Co Nanoparticles for Low‐Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential

Wang,

Fan,

Luan

et al. 2024

Advanced Materials

View full text Add to dashboard Cite

show abstract

Modulating Hydrogen Adsorption by Unconventional p–d Orbital Hybridization over Porous High‐Entropy Alloy Metallene for Efficient Electrosynthesis of Nylon‐6 Precursor

Sheng,

Xie,

Yang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

Renewable electricity driven electrosynthesis of cyclohexanone oxime (C6H11NO) from cyclohexanone (C6H10O) and nitrogen oxide (NOx) is a promising alternative to traditional environment‐unfriendly industrial technologies for green synthesis of C6H11NO. Precisely controlling the reaction pathway of the C6H10O/NOx‐involved electrochemical reductive coupling reaction is crucial for selectively producing C6H11NO, which is yet still challenging. Herein, we report a porous high‐entropy alloy PdCuAgBiIn metallene (HEA‐PdCuAgBiInene) to boost the electrosynthesis of C6H11NO from C6H10O and nitrite, achieving a high Faradaic efficiency (47.6%) and almost 100% yield under ambient conditions. In situ Fourier transform infrared spectroscopy and theoretical calculations demonstrate that unconventional orbital hybridization between d‐block metals and p‐block metals could regulate the local electronic structure of active sites and induce electron localization of electron‐rich Pd sites, which tunes the active hydrogen supply and facilitates the generation and enrichment of key intermediates NH2OH* and C6H10O*, and efficiently promotes their C−N coupling to selectively produce C6H11NO.

show abstract

In situ Generation of Cyclohexanone Drives Electrocatalytic Upgrading of Phenol to Nylon‐6 Precursor

Jia,

Wang,

Jin

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

Coupling in situ generated intermediates with other substrates/intermediates is a viable approach for diversifying product outcomes of catalytic reactions involving two or multiple reactants. Cyclohexanone oxime is a key precursor for caprolactam synthesis (the monomer of Nylon‐6), yet its current production uses unsustainable carbon sources, noble metal catalysts, and harsh conditions. Herein, we report the first work to synthesize cyclohexanone oxime through electroreduction of phenol and hydroxylamine. The Faradaic efficiency reached 69.1% over Cu catalyst, accompanied by a corresponding cyclohexanone oxime formation rate of 82.0 g h‐1 gcat‐1. In addition, the conversion of phenol was up to 97.5%. In situ characterizations, control experiments, and theoretical calculations suggested the importance of balanced activation of water, phenol, and hydroxylamine substrates on the optimal metallic Cu catalyst for achieving high‐performance cyclohexanone oxime synthesis. Besides, a tandem catalytic route for the upgrading of lignin to caprolactam has been successfully developed through the integration of thermal catalysis, electrocatalysis, and Beckmann rearrangement, which achieved the synthesis of 0.40 g of caprolactam from 4.0 g of lignin raw material.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions

Cited by 16 publications

References 69 publications

Ru‐Incorporation‐Induced Phase Transition in Co Nanoparticles for Low‐Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential

Ru‐Incorporation‐Induced Phase Transition in Co Nanoparticles for Low‐Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential

Modulating Hydrogen Adsorption by Unconventional p–d Orbital Hybridization over Porous High‐Entropy Alloy Metallene for Efficient Electrosynthesis of Nylon‐6 Precursor

In situ Generation of Cyclohexanone Drives Electrocatalytic Upgrading of Phenol to Nylon‐6 Precursor

Contact Info

Product

Resources

About

Nitrogenous Intermediates in NOx‐involved Electrocatalytic Reactions

Cited by 16 publications

References 69 publications

Ru‐Incorporation‐Induced Phase Transition in Co Nanoparticles for Low‐Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential

Ru‐Incorporation‐Induced Phase Transition in Co Nanoparticles for Low‐Concentration Nitric Oxide Electroreduction to Ammonia at Low Potential

Modulating Hydrogen Adsorption by Unconventional p–d Orbital Hybridization over Porous High‐Entropy Alloy Metallene for Efficient Electrosynthesis of Nylon‐6 Precursor

In situ Generation of Cyclohexanone Drives Electrocatalytic Upgrading of Phenol to Nylon‐6 Precursor

Contact Info

Product

Resources

About

Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions