Lithium-Mediated Ammonia Electrosynthesis with Ether-Based Electrolytes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(47), С. 25716 - 25725

Опубликована: Ноя. 15, 2023

Ammonia is of great importance in fertilizer production and chemical synthesis. It can also potentially serve as a carbon-free energy carrier for future hydrogen economy. Motivated by worldwide effort to lower carbon emissions, ammonia synthesis lithium-mediated electrochemical nitrogen reduction (LiNR) has been considered promising alternative the Haber-Bosch process. A significant performance improvement LiNR achieved recent years exploration favorable lithium salt proton donor electrolyte recipe, but solvent study still its infancy. In this work, systematic investigation on ether-based solvents toward conducted. The assessments candidates are built their conductivity, parasitic reactions, product distribution, faradaic efficiency. Notably, dimethoxyethane gives lowest potential loss among investigated systems, while tetrahydrofuran achieves an outstanding efficiency 58.5 ± 6.1% at ambient pressure. We found that molecules impact above characteristics dictating solvation configurations conductive ions inducing formation solid interphase with different compositions. This highlights process advances optimization better performance.

Язык: Английский

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Phenol as proton shuttle and buffer for lithium-mediated ammonia electrosynthesis

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 18, 2024

Abstract Ammonia is a crucial component in the production of fertilizers and various nitrogen-based compounds. Now, lithium-mediated nitrogen reduction reaction (Li-NRR) has emerged as promising approach for ammonia synthesis at ambient conditions. The proton shuttle plays critical role transfer process during Li-NRR. However, structure-activity relationship design principles effective shuttles have not yet been established practical Li-NRR systems. Here, we propose general procedure verifying true shuttles. We systematically evaluate several classes continuous-flow reactor with hydrogen oxidation anode. Among tested shuttles, phenol exhibits highest Faradaic efficiency 72 ± 3% towards ammonia, surpassing that ethanol, which commonly used so far. Experimental investigations including operando isotope-labelled mass spectrometry proved proton-shuttling capability phenol. Further transport modeling sheds light on mechanism.

Язык: Английский

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MoS2/Ti3CO2 heterostructure-based ceramics as promising electrode material for high-performance monovalent energy storage devices

Ceramics International, Год журнала: 2023, Номер 50(3), С. 4782 - 4789

Опубликована: Ноя. 20, 2023

Язык: Английский

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Improved Electrochemical Performance of Aqueous Hybrid Supercapacitors Using CrCo₂O₄ Mesoporous Nanowires: An Innovative Strategy toward Sustainable Energy Devices

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(6), С. 6920 - 6930

Опубликована: Фев. 2, 2024

High-rate aqueous hybrid supercapacitors (AHSCs) have attracted relevant scientific significance owing to their expected energy density, supercapacitor-level power and battery-level density. In this work, a bimetallic nanostructured material with chromium-incorporated cobalt oxide (CCO, i.e., CoCr2O4) was prepared via hydrothermal method form stable cubic obelisk structure. Compared CCO materials using traditional methods, displayed nanowire structure (50 nm diameter), suggesting an enhanced specific surface area large number of active sites for chemical reactions. The electrode possessed high capacitance (2951 F g–1) at current density 1 A g–1, minimum Rct (0.135 Ω), the highest retention (98.7%), making it ideal AHSCs. Ex situ analysis based on X-ray diffraction (XRD) photoelectron spectroscopy (XPS) showed favorable stability after 10,000 cycles without any phase changes being detected. GGA + U methods employed in functional theory (DFT) also highlighted metallic properties originating from synergistic effect semiconducting Cr2O3 Co3O4 materials.

Язык: Английский

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Operando investigations of the solid electrolyte interphase in the lithium mediated nitrogen reduction reaction

Energy & Environmental Science, Год журнала: 2024, Номер 17(10), С. 3482 - 3492

Опубликована: Янв. 1, 2024

Operando GI-WAXS showed that the SEI layer formed by LiBF 4 enhances Li-NRR performance limiting proton transport to electrode. Intermediate LiN x H y species give insight into mechanism of Li-NRR.

Язык: Английский

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Core–Shell Engineering Boosted Active Hydrogen Generation in Cu_2–xS/MoS₂ Quantum Dots for Efficient Electrocatalytic Nitrate Reduction to Ammonia

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(15), С. 5979 - 5990

Опубликована: Апрель 1, 2024

The electrochemical nitrate reduction reaction (NO3RR) emerges as a promising method for ammonia (NH3) production, which faces the dilemma of inhibiting hydrogen evolution (HER) and promoting active (Hads) supply hydrogenation nitrogen intermediates. Here, core–shell structure engineering strategy is developed Cu2–xS/MoS2, where strong Hads adsorption storage capacity can accelerate As result, an eminent NH3 yield 0.178 mmol h–1 cm–2 Faradaic efficiency 84.5% were achieved. A series tests demonstrate that tuning Cu2–xS/MoS2 interface improve activity conversion NO2–, while avoiding HER effectively retain Hads. density functional theory calculation further demonstrates has *H retention ability to promote NO3RR process. This work offers novel perspective on manipulation generation NO3RR.

Язык: Английский

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Complete electrocatalytic defluorination of perfluorooctane sulfonate in aqueous solution with nonprecious materials

Journal of Catalysis, Год журнала: 2024, Номер 431, С. 115403 - 115403

Опубликована: Фев. 29, 2024

Perfluorooctane sulfonate (PFOS) was completely defluorinated in aqueous electrocatalysis with laser-made [NiFe]-layered double hydroxide nanocatalysts immobilized on hydrophilic carbon fiber paper anodes. All materials were nonprecious, as needed for globally scalable remediation technologies per- and poly-fluoroalkyl substances (PFAS). Pulsed electrolysis of 0.50 or 0.05 mM PFOS 8.0 M LiOH solution assisted by ultraviolet light irradiation enhanced electrical energy capital expense efficiency compared to existing techniques. Electrocatalytic defluorination occurred within the anode microenvironment, evidenced pulsed vs continuous chronoamperometry data electrolyte agitation experiments. We observed adsorbed surface-bound OOH X-ray photoelectron spectra post-electrocatalysis anodes, corroborating that electrocatalytically regenerated reactive oxygen species microenvironment. High concentrations lithium ions high basicity essential efficient defluorination, which also worked perfluorooctanoic acid (PFOA), albeit more efficiently PFOS, presumably due advanced oxidation processes sulfate radicals near defluorination.

Язык: Английский

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What Metals Should Be Used to Mediate Electrosynthesis of Ammonia from Nitrogen and Hydrogen from a Thermodynamic Standpoint?

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12320 - 12323

Опубликована: Апрель 10, 2024

Recently, metal-mediated electrochemical conversion of nitrogen and hydrogen to ammonia (M-eNRRs) has been attracting intense research attention as a potential route for synthesis under ambient conditions. However, which metals should be used mediate M-eNRRs remains unanswered. This work provides an extensive comparison the energy consumption in classical Haber Bosch (H-B) process M-eNRRs. The results indicate that when employing lithium calcium, popularly M-eNRRs, is more than 10 times greater H-B even assuming 100% Faradaic efficiency zero overpotentials. Only electrosynthesis with cell voltage not exceeding 0.38 V might have rival from energetic perspective. A further analysis other periodic table reveals only some heavy metals, including In, Tl, Co, Ni, Ga, Mo, Sn, Pb, Fe, W, Ge, Re, Bi, Cu, Po, Tc, Ru, Rh, Ag, Hg, Pd, Ir, Pt, Au, can potentially consume less purely thermodynamic standpoint, but whether they activate N

Язык: Английский

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Exploration of Multidimensional Structural Optimization and Regulation Mechanisms: Catalysts and Reaction Environments in Electrochemical Ammonia Synthesis

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

Ammonia (NH3) is esteemed for its attributes as a carbon-neutral fuel and hydrogen storage material, due to high energy density, abundant content, notably higher liquefaction temperature in comparison gas. The primary method the synthetic generation of NH3 Haber-Bosch process, involving rigorous conditions resulting significant global consumption carbon dioxide emissions. To tackle environmental challenges, exploration innovative green sustainable technologies synthesis imperative. Rapid advances electrochemical technology have created fresh prospects researchers realm environmentally friendly synthesis. Nevertheless, intricate intermediate products sluggish kinetics reactions impede progress (EAS) technologies. improve activity selectivity EAS, which encompasses electrocatalytic reduction nitrogen gas, nitrate, nitric oxide, numerous electrocatalysts design strategies been meticulously investigated. Here, this review primarily delves into recent obstacles EAS pathways, examining methods boost yield rate current efficiency via multidimensional structural optimization, while also exploring challenges outlook EAS.

Язык: Английский

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Selectivity Control in the Nitrogen Reduction Reaction over Mo₂C MXene by a Nitrogen-Rich Environment

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5589 - 5600

Опубликована: Март 21, 2025

Язык: Английский

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