Unveiling the Activity Origin of a Copper‐based Electrocatalyst for Selective Nitrate Reduction to Ammonia

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(13), С. 5350 - 5354

Опубликована: Янв. 22, 2020

Abstract Unveiling the active phase of catalytic materials under reaction conditions is important for construction efficient electrocatalysts selective nitrate reduction to ammonia. The origin prominent activity enhancement CuO (Faradaic efficiency: 95.8 %, Selectivity: 81.2 %) toward electroreduction ammonia was probed. 15 N isotope labeling experiments showed that originated from reduction. 1 H NMR spectroscopy and colorimetric methods were performed quantify In situ Raman ex revealed electrochemically converted into Cu/Cu 2 O, which serves as an phase. combined results online differential electrochemical mass spectrometry (DEMS) DFT calculations demonstrated electron transfer Cu O at interface could facilitate formation *NOH intermediate suppress hydrogen evolution reaction, leading high selectivity Faradaic efficiency.

Язык: Английский

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Transition metal nitrides for electrochemical energy applications

Chemical Society Reviews, Год журнала: 2020, Номер 50(2), С. 1354 - 1390

Опубликована: Дек. 10, 2020

This review comprehensively summarizes the progress on structural and electronic modulation of transition metal nitrides for electrochemical energy applications.

Язык: Английский

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Strategies to suppress hydrogen evolution for highly selective electrocatalytic nitrogen reduction: challenges and perspectives

Energy & Environmental Science, Год журнала: 2021, Номер 14(3), С. 1176 - 1193

Опубликована: Янв. 1, 2021

This review underlines the strategies to suppress HER for selective NRR in view of proton-/electron-transfer kinetics, thermodynamics, and electrocatalyst design on basis deep understanding mechanisms.

Язык: Английский

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Comprehensive Understanding of the Thriving Ambient Electrochemical Nitrogen Reduction Reaction

Advanced Materials, Год журнала: 2021, Номер 33(33)

Опубликована: Июль 1, 2021

Abstract The electrochemical method of combining N 2 and H O to produce ammonia (i.e., the nitrogen reduction reaction [E‐NRR]) continues draw attention as it is both environmentally friendly well suited for a progressively distributed farm economy. Despite multitude recent works on E‐NRR, further progress in this field faces bottleneck. On one hand, despite extensive exploration trial‐and‐error evaluation E‐NRR catalysts, no study has stood out become stage protagonist. other current level production (microgram‐scale) an almost insurmountable obstacle its qualitative quantitative determination, hindering discrimination between true activity contamination. Herein i) popular theory mechanism NRR are introduced; ii) comprehensive summary related catalysts provided; iii) operational procedures addressed, including acquisition key metrics, challenges faced, most suitable solutions; iv) guiding principles standardized recommendations emphasized future research directions prospects provided.

Язык: Английский

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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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Electrochemical ammonia synthesis: Mechanistic understanding and catalyst design

Chem, Год журнала: 2021, Номер 7(7), С. 1708 - 1754

Опубликована: Фев. 21, 2021

Язык: Английский

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Ammonia and Nitric Acid Demands for Fertilizer Use in 2050

ACS Energy Letters, Год журнала: 2021, Номер 6(10), С. 3676 - 3685

Опубликована: Сен. 24, 2021

Access to nitrogen-based fertilizers is critical maximize agricultural yield, as nitrogen the most common rate-limiting nutrient. Nearly all rely on ammonia and nitric acid feedstocks, thus demand for these chemicals heavily dependent global population food demand. Over next three decades, will continue dictate market size value acid, which consequently have a significant impact our energy infrastructure. Here, we discuss potential carbon-free electrocatalytic reduction, oxidation, nitrate reduction meet fertilizer manufacturing demands. We also explore various growth scenarios predict 2050 acid. highlight that if current approaches remain constant, carbon emissions from production of fixed feedstocks could exceed 1300 MtCO2eq/yr, prompting strong need green alternatives.

Язык: Английский

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Rational Catalyst Design for N₂ Reduction under Ambient Conditions: Strategies toward Enhanced Conversion Efficiency

ACS Catalysis, Год журнала: 2020, Номер 10(12), С. 6870 - 6899

Опубликована: Май 26, 2020

Ammonia (NH3), one of the basic chemicals in most fertilizers and a promising carbon-free energy storage carrier, is typically synthesized via Haber–Bosch process with high consumption massive emission greenhouse gases. The photo/electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions has attracted increasing interests recently, providing alternative routes to realize green NH3 synthesis. Despite rapid advances achieved this attractive research field, unsatisfactory conversion efficiency including low yield rate, limited Faradaic or apparent quantum still remains as great challenge. NRR performance intrinsically related electronic surface structure catalysts. Rational design preparation advanced catalysts are indispensable improve (e.g., activity selectivity) NRR. In Review, various strategies for development desirable comprehensively summarized, mainly containing defect engineering, structural manipulation, crystallographic tailoring, interface regulation. State-of-the-art heterogeneous catalysts, prevailing theories underlying catalytic mechanisms, together current issues, critical challenges, perspectives discussed. It highly expected that Review will promote understanding recent area stimulate greater designing future.

Язык: Английский

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Identifying the Origin of Ti³⁺ Activity toward Enhanced Electrocatalytic N₂ Reduction over TiO₂ Nanoparticles Modulated by Mixed‐Valent Copper

Advanced Materials, Год журнала: 2020, Номер 32(30)

Опубликована: Июнь 21, 2020

The ambient electrocatalytic N2 reduction reaction (NRR) enabled by TiO2 has attracted extensive recent attention. Previous studies suggest the formation of Ti3+ in can significantly improve NRR activity, but it still remains unclear what kinds are effective. Herein, is demonstrated that mixed-valent Cu acts as an effective dopant to modulate oxygen vacancy (VO ) concentration and formation, which markedly improves performance. In 0.5 m LiClO4 , this electrocatalyst attains a high Faradic efficiency 21.99% large NH3 yield 21.31 µg h-1 mgcat.-1 at -0.55 V vs reversible hydrogen electrode, even surpasses most reported Ti-based electrocatalysts. Using density function theory calculations, evidenced ions (101) surface with multiple vacancies, beneficial for generating different 3d1 defect states localized below Fermi energy. activation adsorption effectively strengthened when present splitting eg t2g orbitals, be modulated its coordination structure. synergistic roles three ion pairs formed VO defect, including Cu1+ -Ti4+ -Ti3+ together responsible enhanced

Язык: Английский

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Electronic Modulation of Non‐van der Waals 2D Electrocatalysts for Efficient Energy Conversion

Advanced Materials, Год журнала: 2021, Номер 33(26)

Опубликована: Май 25, 2021

Abstract The exploration of efficient electrocatalysts for energy conversion is important green development. Owing to their high surface areas and unusual electronic structure, 2D have attracted increasing interest. Among them, non‐van der Waals (non‐vdW) materials with numerous chemical bonds in all three dimensions novel properties beyond those vdW been studied increasingly over the past decades. Herein, progress non‐vdW critically reviewed, a special emphasis on structure modulation. Strategies heteroatom doping, vacancy engineering, pore creation, alloying, heterostructure engineering are analyzed tuning structures achieving intrinsically enhanced electrocatalytic performances. Lastly, roadmap future development provided from material, mechanism, performance viewpoints.

Язык: Английский

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