A phosphorus-doped potassium peroxyniobate electrocatalyst with enriched oxygen vacancies boosts electrocatalytic nitrogen reduction to ammonia

Fan, Shuhui; Zhao, Fang; Wang, Xuansheng; Wang, Qi; Zhao, Qiang; Li, Jinping; Liu, Guang

doi:10.1039/d2dt01501c

Cited by 5 publications

(8 citation statements)

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Section: Methods To Generate Ovs and Applications In Enrrmentioning

confidence: 99%

“…Fan et al synthesized OV-rich P-doped potassium peroxynitrite (KNb 3 O 8 , abbreviated as P-KNO) by a simple solid-phase method followed by phosphorylation ( Fan et al, 2022 ). The NH 3 yield of P-KNO was 23.01 μg h −1 mg −1 (at −0.45 V vs. RHE) and the FE was 39.77% (at −0.4 V vs. RHE) in 0.1 M Na 2 SO 4 electrolyte ( Figure 2F ), which is twice that of unphosphorylated KNO.…”

Section: Methods To Generate Ovs and Applications In Enrrmentioning

confidence: 99%

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Oxygen vacancies engineering in electrocatalysts nitrogen reduction reaction

Zhu

Wang²,

He³

et al. 2022

Front. Chem.

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Ammonia is important, both as a fertilizer and as a carrier of clean energy, mainly produced by the Haber-Bosch process, which consumes hydrogen and emits large amounts of carbon dioxide. The ENRR (Electronchemical Nitrogen Reduction Reaction) is considered a promising method for nitrogen fixation owing to their low energy consumption, green and mild. However, the ammonia yield and Faraday efficiency of the ENRR catalysts are low due to the competitive reaction between HER and NRR, the weak adsorption of N2 andthe strong N≡N triple bond. Oxygen vacancy engineering is the most important method to improve NRR performance, not only for fast electron transport but also for effective breaking of the N≡N bond by capturing metastable electrons in the antibonding orbitals of nitrogen molecules. In this review, the recent progress of OVs (oxygen vacancies) in ENRR has been summarized. First, the mechanism of NRR is briefly introduced, and then the generation methods of OVs and their applicationin NRR are discussed, including vacuum annealing, hydrothermal method, hydrogen reduction, wet chemical reduction, plasma treatment and heterogeneous ion doping. Finally, the development and challenges of OVs in the field of electrochemical nitrogen fixation are presented. This review shows the important areas of development of catalysts to achieve industrially viable NRR.

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Section: Methods To Generate Ovs and Applications In Enrrmentioning

confidence: 99%

Section: Methods To Generate Ovs and Applications In Enrrmentioning

confidence: 99%

Oxygen vacancies engineering in electrocatalysts nitrogen reduction reaction

Zhu

Wang²,

He³

et al. 2022

Front. Chem.

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“…Despite this, the activity of noble metal catalysts for the NRR has been widely explored [7,11] . Another popular approach, a much more promising avenue for NRR noble metal catalysts, is the development of composites that utilize noble metals as the active site, which has been extensively tested [12–24] . These catalysts are, however, still expensive to manufacture and do not display the necessary activity, therefore, much effort has been given to the investigation of NRR electrocatalysts comprised of earth‐abundant substitutes [25,38] .…”

Section: Introductionmentioning

confidence: 99%

“…[7,11] Another popular approach, a much more promising avenue for NRR noble metal catalysts, is the development of composites that utilize noble metals as the active site, which has been extensively tested. [12][13][14][15][16][17][18][19][20][21][22][23][24] These catalysts are, however, still expensive to manufacture and do not display the necessary activity, therefore, much effort has been given to the investigation of NRR electrocatalysts comprised of earth-abundant substitutes. [25,38] Transition metals (TMs) are a good example of a cheap replacement for the noble metal catalyst.…”

Section: Introductionmentioning

confidence: 99%

Nitrogen Reduction Reaction to Ammonia on Transition Metal Carbide Catalysts

Ellingsson,

Iqbal,

Skúlason

et al. 2023

ChemSusChem

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The development of a low‐cost, energy‐efficient, and environmentally friendly alternative to the currently utilized Haber‐Bosch process to produce ammonia is of great importance. Ammonia is an essential chemical used in fertilizers and a promising high‐density fuel source. The nitrogen reduction reaction (NRR) has been explored intensively as a potential avenue for ammonia production using water as proton source, but to this day a catalyst capable of producing this chemical at high Faradaic efficiency (FE) and commercial yield and rates has not been reported. Here, we investigate the activity of transition metal carbide (TMC) surfaces in the (100) facets of the rocksalt (RS) structure as potential catalysts for the NRR. In this study, we use density functional theory (DFT) to model reaction pathways, estimate stability, assess kinetic barriers, and compare adsorbate energies to determine the overall performance of each TMC surface. For pristine TMC surfaces (with no defects) we find that none of the studied TMCs possess both exergonic adsorption of nitrogen and the capability to selectively protonate nitrogen to form ammonia in the desired aqueous solution. ZrC, however, is shown to be a potential catalyst if used in a non‐aqueous electrolyte. To circumvent the endergonic adsorption of nitrogen onto the surface, a carbon vacancy was introduced. This provides a well‐defined high coordination active site on the surface. In the presence of a vacancy VC, NbC, and WC showed efficient nitrogen adsorption, selectivity towards ammonia, and a low overpotential (OP). NbC did, however, display an unfeasible kinetic barrier to nitrogen dissociation for ambient‐condition purposes, and thus it is suggested for high tempearture/pressure ammonia synthesis. Both WC and VC in their RS (100) structure are promising materials for experimental investigations in aqueous electrolytes, and ZrC could potentially be interesting for non‐aqueous electrolytic systems.

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“…The inert N 2 molecule possesses high first bond breaking energy, ionization potential (15.6 eV), an ultra-stable NuN bond and a large binding energy. 7,8 The high bonding energy of nitrogen makes electrocatalysts critical in the NRR process to increase product efficiency, activity and selectivity. 9,10 The competing hydrogen-evolution reaction (HER) strongly reduces Faraday efficiency (FE).…”

Section: Introductionmentioning

confidence: 99%