A Spectroscopic Study on Nitrogen Electrooxidation to Nitrate

Li, Tieliang; Han, Shuhe; Wang, Yuting; Zhou, Jin; Zhang, Bin; Yu, Yifu

doi:10.1002/anie.202217411

Cited by 14 publications

(18 citation statements)

References 53 publications

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“…ATR–FTIR spectroscopy was analyzed to assign various bonds present after electrolysis with different potentials in the electrolyte medium (Figure S38). − …”

Section: Resultsmentioning

confidence: 99%

Selective Electrocatalytic Oxidation of Nitrogen to Nitric Acid Using Manganese Phthalocyanine

Adalder

Paul

Ghorai

et al. 2023

ACS Appl. Mater. Interfaces

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Ammonia is produced through the energy-intensive Haber–Bosch process, which undergoes catalytic oxidation for the production of commercial nitric acid by the senescent Ostwald process. The two energy-intensive industrial processes demand for process sustainability. Hence, single-step electrocatalysis offers a promising approach toward a more environmentally friendly solution. Herein, we report a 10-electron pathway associated one-step electrochemical dinitrogen oxidation reaction (N2OR) to nitric acid by manganese phthalocyanine (MnPc) hollow nano-structures under ambient conditions. The catalyst delivers a nitric acid yield of 513.2 μmol h–1 gcat –1 with 33.9% Faradaic efficiency @ 2.1 V versus reversible hydrogen electrode. The excellent N2OR performances are achieved due to the specific-selectivity, presence of greater number of exposed active sites, recyclability, and long period stability. The extended X-ray absorption fine structure confirms that Mn atoms are coordinated to the pyrrolic and pyridinic nitrogen via Mn–N4 coordination. Density functional theory-based theoretical calculations confirm that the Mn–N4 site of MnPc is the main active center for N2OR, which suppresses the oxygen evolution reaction. This work provides a new arena about the successful example of one step nitric acid production utilizing a Mn–N4 active site-based metal phthalocyanine electrocatalyst by dinitrogen oxidation for the development of a carbon-neutral sustainable society.

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“…ATR–FTIR spectroscopy was analyzed to assign various bonds present after electrolysis with different potentials in the electrolyte medium (Figure S38). − …”

Section: Resultsmentioning

confidence: 99%

Selective Electrocatalytic Oxidation of Nitrogen to Nitric Acid Using Manganese Phthalocyanine

Adalder

Paul

Ghorai

et al. 2023

ACS Appl. Mater. Interfaces

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“…In addition, there should be more advanced in situ characterization methods to detect reactive intermediates and further support the DFT simulated mechanisms, such as electrochemical in situ differential electrochemical mass spectrometry, electrochemical in situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) and in situ Fourier transformed infrared spectroscopy measurements [31,32] . Currently, in situ characterizations in electrochemical ammonia synthesis are inadequate.…”

Section: Reverse Artificial Nitrogen Cyclementioning

confidence: 99%

“…Fourier transformed infrared spectroscopy measurements. [31,32] Currently, in situ characterizations in electrochemical ammonia synthesis are inadequate.…”

Section: In Situmentioning

confidence: 99%

Activity Trend and Selectivity of Electrochemical Ammonia Synthesis in Reverse Artificial Nitrogen Cycle

Liu

Xiao

2023

ChemSusChem

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Ammonia is important for modern agriculture and food production as it is a major source of fertilizer. Electrochemical ammonia synthesis (EAS) with sustainable energy generated electricity and decentralized reactors has been considered as environmentally friendly process. Several nitrogen sources have been considered and intensively studied in experiments and computations. Recently, it has been proposed and demonstrated that nitrogen oxides (NOx) electroreduction for selective ammonia production is feasible. Fundamental insights on experimental observation are necessary for more rational design of catalysts and reactors in the future. In this concept, we review the theoretical and computational insights of electrochemical nitrogen oxides reduction, particularly, the activity trend over diverse transition metal catalysts and products selectivity at varying potentials. Finally, we address the opportunities and challenges in the reverse artificial nitrogen cycle, as well as fundamental issues in electrochemical reaction modelling.

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“…3−5 The plasmonic metal can be concurrently used as the working electrode in the system enabling an easy coupling with electrochemical methods. 1−4 Electrochemical ATR-SEIRAS has been used for investigating electrocatalysis, 6,7 detecting reaction intermediates, 8 and the characterization of adsorbed species 9,10 due to its unique ability to amplify interfacial phenomena over those occurring at the diffusion layer or bulk phase within the electrochemical cell. 4 However, electrochemical ATR-SEIRAS literature has predominantly focused on processes at plasmonic metallic interfaces.…”

Section: ■ Introductionmentioning

confidence: 99%

Monitoring SEIRAS on a Graphitic Electrode for Surface-Sensitive Electrochemistry: Real-Time Electrografting

Siddiqui,

N’Diaye,

Martin

et al. 2024

Anal. Chem.

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The ubiquity of graphitic materials in electrochemistry makes it highly desirable to probe their interfacial behavior under electrochemical control. Probing the dynamics of molecules at the electrode/electrolyte interface is possible through spectroelectrochemical approaches involving surface-enhanced infrared absorption spectroscopy (SEIRAS). Usually, this technique can only be done on plasmonic metals such as gold or carbon nanoribbons, but a more convenient substrate for carbon electrochemical studies is needed. Here, we expanded the scope of SEIRAS by introducing a robust hybrid graphene-on-gold substrate, where we monitored electrografting processes occurring at the graphene/ electrolyte interface. These electrodes consist of graphene deposited onto a roughened gold-sputtered internal reflection element (IRE) for attenuated total reflectance (ATR) SEIRAS. The capabilities of the graphene-gold IRE were demonstrated by successfully monitoring the electrografting of 4-amino-2,2,6,6-tetramethyl-1-piperidine Noxyl (4-amino-TEMPO) and 4-nitrobenzene diazonium (4-NBD) in real time. These grafts were characterized using cyclic voltammetry and ATR-SEIRAS, clearly showing the 1520 and 1350 cm −1 NO 2 stretches for 4-NBD and the 1240 cm −1 C−C, C− C−H, and N−O ̇stretch for 4-amino-TEMPO. Successful grafts on graphene did not show the SEIRAS effect, while grafting on gold was not stable for TEMPO and had poorer resolution than on graphene-gold for 4-NBD, highlighting the uniqueness of our approach. The graphene-gold IRE is proficient at resolving the spectral responses of redox transformations, unambiguously demonstrating the real-time detection of surface processes on a graphitic electrode. This work provides ample future directions for real-time spectroelectrochemical investigations of carbon electrodes used for sensing, energy storage, electrocatalysis, and environmental applications.

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A Spectroscopic Study on Nitrogen Electrooxidation to Nitrate

Cited by 14 publications

References 53 publications

Selective Electrocatalytic Oxidation of Nitrogen to Nitric Acid Using Manganese Phthalocyanine

Selective Electrocatalytic Oxidation of Nitrogen to Nitric Acid Using Manganese Phthalocyanine

Activity Trend and Selectivity of Electrochemical Ammonia Synthesis in Reverse Artificial Nitrogen Cycle

Monitoring SEIRAS on a Graphitic Electrode for Surface-Sensitive Electrochemistry: Real-Time Electrografting

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