Atomic coordination environment engineering of bimetallic alloy nanostructures for efficient ammonia electrosynthesis from nitrate

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(32)

Опубликована: Июль 31, 2023

Electrochemical nitrate reduction reaction (NO 3 RR) to ammonia has been regarded as a promising strategy balance the global nitrogen cycle. However, it still suffers from poor Faradaic efficiency (FE) and limited yield rate for production on heterogeneous electrocatalysts, especially in neutral solutions. Herein, we report one-pot synthesis of ultrathin nanosheet-assembled RuFe nanoflowers with low-coordinated Ru sites enhance NO RR performances electrolyte. Significantly, exhibit outstanding FE 92.9% 38.68 mg h −1 cat (64.47 ) at −0.30 −0.65 V (vs. reversible hydrogen electrode), respectively. Experimental studies theoretical calculations reveal that are highly electroactive an increased d-band center guarantee efficient electron transfer, leading low energy barriers reduction. The demonstration rechargeable zinc-nitrate batteries large-specific capacity using indicates their great potential next-generation electrochemical systems.

Язык: Английский

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A Bi‐Co Corridor Construction Effectively Improving the Selectivity of Electrocatalytic Nitrate Reduction toward Ammonia by Nearly 100%

Advanced Materials, Год журнала: 2023, Номер 35(48)

Опубликована: Сен. 22, 2023

Improving the selective ammonia production capacity of electrocatalytic nitrate reduction reaction (NO3 RR) at ambient conditions is critical to future development and industrial application electrosynthesis ammonia. However, involves multi-proton electron transfer as well desorption underutilization intermediates, posing a challenge selectivity NO3 RR. Here electrodeposition site Co modulated by depositing Bi bottom catalyst, thus obtaining Co+Bi@Cu NW catalyst with Bi-Co corridor structure. In 50 mm NO3- , exhibits highest Faraday efficiency ≈100% (99.51%), an yield rate 1858.2 µg h-1 cm-2 high repeatability -0.6 V versus reversible hydrogen electrode. Moreover, change NO2- concentration on surface observed in situ reflection absorption imaging intermediates RR process detected electrochemical Raman spectroscopy together verify trapping effect It believed that measure modulating deposition loading element easy-to-implement general method for improving NH3 corresponding scientific research applications.

Язык: Английский

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Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia

Advanced Materials, Год журнала: 2024, Номер 36(14)

Опубликована: Янв. 26, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) toward ammonia synthesis is recognized as a sustainable strategy to balance the global nitrogen cycle. However, it still remains great challenge achieve highly efficient production due complex proton‐coupled electron transfer process in NO RR. Here, controlled of RuMo alloy nanoflowers (NFs) with unconventional face‐centered cubic (fcc) phase and hexagonal close‐packed/fcc heterophase for RR reported. Significantly, fcc NFs demonstrate high Faradaic efficiency 95.2% large yield rate 32.7 mg h −1 cat at 0 −0.1 V (vs reversible hydrogen electrode), respectively. In situ characterizations theoretical calculations have unraveled that possess highest d‐band center superior electroactivity, which originates from strong Ru─Mo interactions intrinsic activity phase. The optimal electronic structures supply adsorption key intermediates suppression competitive evolution, further determines remarkable performance. successful demonstration high‐performance zinc‐nitrate batteries suggests their substantial application potential electrochemical energy systems.

Язык: Английский

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H* Species Regulation by Mn‐Co(OH)₂ for Efficient Nitrate Electro‐reduction in Neutral Solution

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 23, 2024

Abstract During the electrocatalytic NO 3 − reduction reaction (NO RR) under neutral condition, activation of H 2 O to generate H* and inhibition inter‐H* species binding, are critically important but remain challenging for suppressing non‐desirable hydrogen evolution (HER). Here, a Mn‐doped Co(OH) (named as Mn‐Co(OH) ) has been synthesized by in situ reconstruction electrolyte, which is able dissociate molecules inhibits binding between each other owing increased interatomic spacing Mn‐doping. The electrocatalyst offers faradaic efficiency (FE) high 98.9±1.7% at −0.6 V vs. reversible electrode (RHE) an energy (EE) 49.90±1.03% NH production RR, among highest recently reported state‐of‐the‐art catalysts electrolyte. Moreover, negligible degradation −200 mA cm −2 found least 500 h, longest catalytic durations ever reported. This work paves novel approach design synthesis efficient RR electrocatalysts.

Язык: Английский

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Strategies and applications of electrocatalytic nitrate reduction towards ammonia

Coordination Chemistry Reviews, Год журнала: 2024, Номер 506, С. 215723 - 215723

Опубликована: Фев. 26, 2024

Язык: Английский

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Boosting Nitrate to Ammonia via the Optimization of Key Intermediate Processes by Low‐Coordinated Cu–Cu Sites

Advanced Functional Materials, Год журнала: 2024, Номер 34(24)

Опубликована: Янв. 17, 2024

Abstract The electrochemical reduction of nitrate to ammonia (NO 3 RR) has emerged as a promising but challenging orientation in sustainable development. Cu is one the most effective NO RR catalysts. However, accumulation 2 − on their surface erected bars further improvement efficiency. Herein, Cu‐based electrocatalyst with low‐coordinated atoms (Cu‐LC) synthesized via instantaneous ablation and rapid cooling target by pulse laser proposed new electrocatalyst, which exhibits enhanced activity NH selectivity 97.01%, yield rate 0.624 mmol h −1 cm −2 at −0.8 V versus RHE long‐term durability, superior reported introduction sites upshifts d‐band center near Fermi Level, enhancing adsorption key intermediates ( * , NO) RR, also effectively regulating generation hydrogenation process, inhibiting Cu‐LC surface, thus achieving efficient production. Furthermore, when evaluated cathode material Zn–NO battery, an open circuit voltage 1.3 power density 3.1 mW are achieved Cu‐LC‐based highlighting multifunctional system for production energy supply.

Язык: Английский

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Boosting Hydrogen Adsorption via Manipulating the d-Band Center of Ferroferric Oxide for Anion Exchange Membrane-Based Seawater Electrolysis

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6981 - 6991

Опубликована: Апрель 19, 2024

Ferroferric oxide-based electrocatalysts are widely applied as hydrogen evolution reaction (HER) catalysts due to their low cost and good electrical conductivity, but they tend exhibit slow adsorption kinetics for HER poison by corrosive Cl– alkaline seawater splitting. In this regard, we report a nanosheet-like catalyst constructed decorating Fe3O4 with Ru P dual doping (Ru/P–Fe3O4@IF). situ characterization density functional theory (DFT) calculations demonstrate that the resulting Ru/P–Fe3O4@IF shows enhanced strength coverage thermal neutral free energy of adsorbed H (ΔGH*) modulating d-band center Fe3O4. Moreover, Ru/P moving up center, weak makes on active sites be avoided in Benefiting from above, exhibits superior performance commercial Pt/C overpotentials only −46 −144 mV reach 100 1000 mA cm–2, respectively. addition, AEM electrolyzer assembled Ru/P–Fe3O4 requires 1.93 V (cell voltage) drive current 2 A cm–2 can maintain stable operation more than h at 500

Язык: Английский

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Grain boundary engineering: An emerging pathway toward efficient electrocatalysis

InfoMat, Год журнала: 2024, Номер 6(8)

Опубликована: Июль 16, 2024

Abstract Electrochemical transformation processes involving carbon, hydrogen, oxygen, nitrogen, and small‐molecule chemistries represent a promising means to store renewable energy sources in the form of chemical energy. However, their widespread deployment is hindered by lack efficient, selective, durable, affordable electrocatalysts. Recently, grain boundary (GB) engineering as one category defect engineering, has emerged viable powerful pathway achieve improved electrocatalytic performances. This review presents timely comprehensive overview recent advances GB for efficient electrocatalysis. The beneficial effects introducing GBs into electrocatalysts are discussed, followed an synthesis characterization GB‐enriched Importantly, latest developments leveraging enhanced electrocatalysis thoroughly examined, focusing on electrochemical utilization cycles nitrogen. Future research directions proposed further advance understanding application image

Язык: Английский

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Enhancement of Nitrate‐to‐Ammonia on Amorphous CeO_x‐Modified Cu via Tuning of Active Hydrogen Supply

Advanced Energy Materials, Год журнала: 2023, Номер 14(7)

Опубликована: Дек. 22, 2023

Abstract The electrochemical nitrate reduction reaction (NO 3 RR) is an environment‐friendly and promising alternative to the conventional Haber–Bosch ammonia synthesis process, which a complex process of proton‐coupled electron transfer. Hereon, amorphous CeO x support introduced construct Cu/a‐CeO heterostructure prepared provide sufficient *H synergistically catalyze NO RR. achieves maximum yield 1.52 mmol h −1 mg cat . In flow cell, NH reaches 17.93 at 1 A cm −2 , exceeds most state‐of‐the‐art catalysts. situ X‐ray diffraction (XRD) in Raman observe that catalyst undergoes structural reconfiguration under operating conditions, thus confirming Cu 2 O not true active center catalytic process. Furthermore, characterizations density functional theory (DFT) calculations demonstrate modulates electronic structure overcomes higher potential barrier required for decomposition water on Cu, greatly facilitates hydrolysis provides H‐coverage rate hydrogenation − realizing dynamic equilibrium between production consumption hydrogen. This component design strategy centered opens up new pathway

Язык: Английский

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Electrocatalytic Nitrate Reduction on Metallic CoNi‐Terminated Catalyst with Industrial‐Level Current Density in Neutral Medium

Advanced Materials, Год журнала: 2024, Номер 36(30)

Опубликована: Май 9, 2024

Abstract Green ammonia synthesis through electrocatalytic nitrate reduction reaction (eNO 3 RR) can serve as an effective alternative to the traditional energy‐intensive Haber‐Bosch process. However, achieving high Faradaic efficiency (FE) at industrially relevant current density in neutral medium poses significant challenges eNO RR. Herein, with guidance of theoretical calculation, a metallic CoNi‐terminated catalyst is successfully designed and constructed on copper foam, which achieves FE up 100% under industrial‐level very low overpotential (−0.15 V versus reversible hydrogen electrode) medium. Multiple characterization results have confirmed that maintained metal atom‐terminated surface interaction atoms plays crucial role reducing density. By constructing homemade gas stripping absorption device, complete conversion process for high‐purity ammonium products demonstrated, displaying potential practical application. This work suggests sustainable promising toward directly converting nitrate‐containing pollutant solutions into nitrogen fertilizers.

Язык: Английский

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