Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Deleted Journal, Год журнала: 2022, Номер 1, С. e9120010 - e9120010

Опубликована: Май 30, 2022

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 minimal carbon emissions. The background of such N-cycles, as fixation, ammonia oxidation, nitrate reduction, is briefly introduced here. discussion emerging nanostructures in various conversion reactions focused on architecture/compositional design, electrochemical performances, reaction mechanisms, instructive tests. Energy device advancements for achieving more functions well in situ/operando characterizations toward understanding key steps are also highlighted. Furthermore, some recently proposed less discussed C–N coupling summarized. We classify inorganic sources that each other under an applied voltage into three types, namely, abundant nitrogen, toxic (nitrite), oxides, useful compounds ammonia, hydrazine, hydroxylamine, goal providing critical insights strategies facilitate development our circular economy.

Язык: Английский

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Theoretical Insights into Superior Nitrate Reduction to Ammonia Performance of Copper Catalysts

ACS Catalysis, Год журнала: 2021, Номер 11(23), С. 14417 - 14427

Опубликована: Ноя. 15, 2021

Nitrate reduction to ammonia (NRA) is critical and attractive for environmental remediation energy conservation. Copper represents one of the most promising non-noble-metal NRA electrocatalysts while its intrinsic catalytic activity facets pH influence remain unclear. Using density functional theory calculations, nitrate pathways are evaluated on low-index crystal surfaces, Cu(111), Cu(100), Cu(110), at different pH. Systematic thermodynamic kinetic analysis indicates that pathway NO3– → *NO3 *NO2 *NO *NOH *NHOH *NH *NH2 *NH3 NH3(g) probable in all ranges, ending a long-standing debate pathways. Both deoxygenation hydrogenation processes substantially affected by Thus, rate-determining steps overpotentials exhibit pH-dependent characteristics. Besides, it found influences competition between hydrogen evolution reaction (HER) NRA. By considering HER we Cu(100) Cu(111) contribute other than Cu(110). Specifically, near-neutral alkaline environments, exhibits best NH3 performance, more effective strong acidic environment. This result rationalizes recent experimental observations. The differences copper surfaces attributed local coordination environment electronic states surface atoms. Thanks stereospecific Cu–Cu couple, both adsorption weak realized facilitating superior

Язык: Английский

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Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction

Chem, Год журнала: 2023, Номер 9(7), С. 1768 - 1827

Опубликована: Июнь 21, 2023

Язык: Английский

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Elucidating the activity, mechanism and application of selective electrosynthesis of ammonia from nitrate on cobalt phosphide

Energy & Environmental Science, Год журнала: 2021, Номер 15(2), С. 760 - 770

Опубликована: Дек. 17, 2021

Cobalt phosphide is an effective electrocatalyst for NO 3 − electroreduction into NH . Phosphorus crucial stabilizing the active phase and optimizing energy barriers, Co 4p orbitals directly participate in nitrate reduction.

Язык: Английский

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Metallic Co Nanoarray Catalyzes Selective NH₃ Production from Electrochemical Nitrate Reduction at Current Densities Exceeding 2 A cm⁻²

Advanced Science, Год журнала: 2021, Номер 8(7)

Опубликована: Фев. 1, 2021

Abstract Electrochemical nitrate reduction (NITRR) offers a promising alternative toward nitrogen recycling and ammonia production under ambient conditions, for which highly active selective electrocatalyst is desired. In this study, metallic cobalt nanoarrays as facilely prepared from the electrochemical of Co(OH) 2 (NAs) are demonstrated to exhibit unprecedented NH 3 producing capability catalyzing NITRR. Benefitting high intrinsic activity Co 0 , intimate contact between species conductive substrate nanostructure exposes large number sites, Co‐NAs electrode exhibits current density −2.2 A cm −2 rate 10.4 mmol h −1 at −0.24 V versus RHE alkaline condition significantly surpasses reported counterparts. Moreover, close‐to‐unity (≥96%) Faradaic efficiency (FE) achieved over wide application range (potential, NO − concentration pH). Density function theory calculation reveals optimized adsorption energy NITRR intermediates on surface . Furthermore, it proposed that despite sluggish kinetics Volmer step (H O → *H + *OH) provides protons in conventional hydrogenation mechanism, proton‐supplying water dissociation process drastically facilitated following concerted dissociation–hydrogenation pathway.

Язык: Английский

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Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate–ammonia conversion

Energy & Environmental Science, Год журнала: 2021, Номер 14(9), С. 4989 - 4997

Опубликована: Янв. 1, 2021

An intermediate-mediated approach was proposed to synthesize copper, rich in (100) facets and defects, for highly efficient nitrate reduction.

Язык: Английский

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Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

Advanced Materials, Год журнала: 2023, Номер 36(17)

Опубликована: Июнь 9, 2023

Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N-containing fertilizers induces the increase nitrate level in surface and ground waters, substantial emission oxides causes heavy air pollution. Nitrogen gas, as main component air, used for mass ammonia production over a century, providing enough nutrition agriculture to support world population increase. In last decade, researchers have made great efforts develop processes under ambient conditions combat intensive energy consumption high carbon associated with Haber-Bosch process. Among different techniques, electrochemical reduction reaction (NO

Язык: Английский

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Coordination Symmetry Breaking of Single‐Atom Catalysts for Robust and Efficient Nitrate Electroreduction to Ammonia

Advanced Materials, Год журнала: 2022, Номер 34(36)

Опубликована: Июль 16, 2022

Nitrate electrocatalytic reduction (NO3 RR) for ammonia production is a promising strategy to close the N-cycle from nitration contamination, as well an alternative Haber-Bosch process with less energy consumption and carbon dioxide release. However, current long-term stability of NO3 RR catalysts usually tens hours, far requirements industrialization. Here, symmetry-broken Cusingle-atom are designed, catalytic activity retained after operation more than 2000 h, while average rate 27.84 mg h-1 cm-2 at industrial level density 366 mA achieved, obtaining good balance between stability. Coordination symmetry breaking achieved by embedding one Cu atom in graphene nanosheets two N O atoms cis-configuration, effectively lowering coordination symmetry, rendering active site polar, accumulating NO3- near electrocatalyst surface. Additionally, cis-coordination splits 3d orbitals, which generates orbital-symmetry-matched π-complex key intermediate *ONH reduces barrier, compared σ-complex generated other catalysts. These results reveal critical role single-atom catalysts, prompting design coordination-symmetry-broken electrocatalysts toward possible

Язык: Английский

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Regulating active hydrogen adsorbed on grain boundary defects of nano-nickel for boosting ammonia electrosynthesis from nitrate

Energy & Environmental Science, Год журнала: 2023, Номер 16(6), С. 2611 - 2620

Опубликована: Янв. 1, 2023

The grain boundary defect engineered Ni nanoparticles has been explored for boosting selective nitrate electroreduction to ammonia, and its NH 3 generation rate is much higher than those of the reported copper or noble metal-based catalysts.

Язык: Английский

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Regulating surface oxygen species on copper (I) oxides via plasma treatment for effective reduction of nitrate to ammonia

Applied Catalysis B Environment and Energy, Год журнала: 2021, Номер 305, С. 121021 - 121021

Опубликована: Дек. 18, 2021

Язык: Английский

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