Enabled Efficient Ammonia Synthesis and Energy Supply in a Zinc–Nitrate Battery System by Separating Nitrate Reduction Process into Two Stages

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Feb. 2, 2023

The aqueous electrocatalytic reduction of NO3- into NH3 (NitrRR) presents a sustainable route applicable to production and potentially energy storage. However, the NitrRR involves directly eight-electron transfer process generally required large overpotential (<-0.2 V versus reversible hydrogen electrode (vs. RHE)) reach optimal efficiency. Here, inspired by biological nitrate respiration, was separated two stages along [2+6]-electron pathway alleviate kinetic barrier. system employed Cu nanowire catalyst produces NO2- with current efficiencies 91.5 % 100 %, respectively at lower overpotentials (>+0.1 vs. RHE). high efficiency for such further explored in zinc-nitrate battery. This battery could be specified output voltage 0.70 V, an average density 566.7 Wh L-1 10 mA cm-2 power 14.1 mW , which is well beyond all previously reported similar concepts.

Language: Английский

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Recent progress and strategies on the design of catalysts for electrochemical ammonia synthesis from nitrate reduction

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3489 - 3514

Published: Jan. 1, 2023

Ammonia (NH3) is an essential raw material in the production of fertilizers and a promising carbon-free energy carrier, however, its synthesis still depends on energy- capital-intensive Haber–Bosch process. Recently, electrochemical N2 reduction reaction has attracted significant interest as emerging method for NH3 under ambient conditions. However, limited solubility aqueous electrolyte strong NN bonds result low yield rate, inferior faradaic efficiency unsatisfactory selectivity, impeding further practical application. Considering high water nitrate (NO3−), NO3− (NO3−RR) become fascinating route achieving sustainable NH3, enormous progress been made this field. As consequence, review discusses mechanism systematically summarizes recent development electrocatalysts NO3−RR, including noble-metal-based materials, single-atom metal catalysts, transition-metal-based catalysts. Diverse design strategies catalysts to boost NO3−RR performance, such defect engineering, rational structure design, strain engineering constructing heterostructures, are discussed. This followed by illustration how robust understanding optimization affords fundamental insights into efficiency, selectivity electrocatalysts. Finally, we conclude with future perspectives critical issues, challenges research directions high-efficiency selective NH3.

Language: Английский

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Electro-triggered Joule heating method to synthesize single-phase CuNi nano-alloy catalyst for efficient electrocatalytic nitrate reduction toward ammonia

Nano Research, Journal Year: 2023, Volume and Issue: 16(5), P. 6632 - 6641

Published: March 20, 2023

Language: Английский

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Self‐Supported Pd Nanorod Arrays for High‐Efficient Nitrate Electroreduction to Ammonia

Small, Journal Year: 2023, Volume and Issue: 19(10)

Published: Jan. 22, 2023

Electrochemical nitrate (NO3- ) reduction to ammonia (NH3 offers a promising pathway recover NO3- pollutants from industrial wastewater that can balance the nitrogen cycle and sustainable green NH3 production. However, efficiency of electrocatalytic synthesis remains low for most electrocatalysts due complex reaction processes severe hydrogen precipitation reaction. Herein, high performance RR) is demonstrated on self-supported Pd nanorod arrays in porous nickel framework foam (Pd/NF). It provides lot active sites H* adsorption activation leading remarkable yield rate 1.52 mmol cm-2 h-1 Faradaic 78% at -1.4 V versus RHE. Notably, it maintains over 50 cycles 25 h showing good stability. Remarkably, large-area Pd/NF electrode (25 cm2 shows 174.25 mg , be candidate device application. In situ FTIR spectroscopy density functional theory calculations analysis confirm enrichment effect nanorods encourages H species following hydrogenation mechanism. This work brings useful strategy designing RR catalysts with customizable compositions.

Language: Английский

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Rare earth oxide based electrocatalysts: synthesis, properties and applications

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 714 - 763

Published: Dec. 18, 2023

The synthesis, properties and applications of rare earth oxide based electrocatalysts in electrocatalysis reactions.

Language: Английский

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Electrocatalytic nitrate-to-ammonia conversion on CoO/CuO nanoarrays using Zn–nitrate batteries

Nanoscale, Journal Year: 2023, Volume and Issue: 15(48), P. 19577 - 19585

Published: Jan. 1, 2023

Zn-NO3- batteries can generate electricity while producing NH3 in an environmentally friendly manner, making them a very promising device. However, the conversion of NO3- to involves proton-assisted 8-electron (8e-) transfer process with high kinetic barrier, requiring high-performance catalysts realize potential applications this technology. Herein, we propose heterostructured CoO/CuO nanoarray electrocatalyst prepared on copper foam (CoO/CuO-NA/CF) that electrocatalytically and efficiently convert at low achieves maximum yield 296.9 μmol h-1 cm-2 Faraday efficiency (FE) 92.9% -0.2 V vs. reversible hydrogen electrode (RHE). Impressively, battery based monolithic CoO/CuO-NA/CF delivers 60.3 cm-2, FENH3 82.0%, power density 4.3 mW cm-2. This study provides paradigm for catalyst preparation energy-efficient production simultaneously generating electrical energy.

Language: Английский

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Oxygen Vacancies‐Rich Metal Oxide for Electrocatalytic Nitrogen Cycle

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 13, 2023

Abstract The development of industry and agriculture has been accompanied by an artificially imbalanced nitrogen cycle, which threatens human health ecological environments. Electrocatalytic systems have emerged as a sustainable way converting nitrogen‐containing molecules into high value‐added chemicals. However, the construction high‐performance electrocatalysts remains challenging. oxygen vacancy engineering strategy promoted more research efforts to explore structure‐activity relationship between catalytic activity vacancies. This review systematically summarizes recent vacancies‐rich metal oxides for electro‐catalyzing cycling systems, involving electrocatalytic nitrate reduction reaction, nitric oxide C─N coupling, urea oxidation reaction. First, methods characterization vacancies are summarized. Then, effect on is discussed in terms regulating electronic structures electrocatalysts, improving electroconductivity catalysts, lowing energy barrier, strengthening adsorption activation intermediate species. Finally, future directions cycle anticipated.

Language: Английский

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

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(30)

Published: May 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.

Language: Английский

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Surface Oxygen Vacancies Induced by Calcium Substitution in Macroporous La₂Ce_2–xCa_xO_7−δ Catalysts for Boosting Low-Temperature Oxidative Coupling of Methane

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1882 - 1902

Published: Jan. 20, 2024

Surface oxygen vacancies in the catalysts play a key role improving catalytic performances for low-temperature oxidative coupling of methane (OCM). Herein, macroporous La2Ce2–xCaxO7−δ (A2B2O7-type) with disordered defective cubic fluorite phased structure were prepared by citric acid sol–gel method. The improved accessibility reactants (O2 and CH4) to active sites. partial substitution B site (Ce) low-valence calcium (Ca) ions induced formation surface vacancies, which facilitated adsorption activation O2 molecules generate species (O2– species). O2– can boost CH4 govern following step dehydrogenation C2H6 C2H4. have high activity OCM, La2Ce1.3Ca0.7O7−δ catalyst highest density exhibits during OCM into C2H4 (C2) products, i.e., its conversion, selectivity, yield C2 products at 600 °C are 31.0, 65.6, 20.3%, respectively. Based on results multiple experimental characterizations functional theory calculations, mechanism reaction is proposed: Ce Ca significantly promote critical steps C–H bond breaking C–C reaction. It important design high-efficiency practical applications.

Language: Английский

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In Situ Growth of Fe₂O₃ Nanorod Arrays on Carbon Cloth with Rapid Charge Transfer for Efficient Nitrate Electroreduction to Ammonia

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(44), P. 49765 - 49773

Published: Oct. 25, 2022

Electrochemical reduction of nitrate to ammonia (NH

Language: Английский

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