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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Urea Electrosynthesis from Nitrate and CO₂ on Diatomic Alloys

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

Опубликована: Июнь 14, 2024

Abstract Urea electrosynthesis from co–electrolysis of NO 3 − and CO 2 (UENC) offers a promising technology for achieving sustainable efficient urea production. Herein, diatomic alloy catalyst (CuPd 1 Rh –DAA), with mutually isolated Pd atoms alloyed on Cu substrate, is theoretically designed experimentally confirmed to be highly active selective UENC catalyst. Combining theoretical computations operando spectroscopic characterizations reveals the synergistic effect –Cu sites promote via tandem catalysis mechanism, where site triggers early C–N coupling promotes *CO –to–*CO NH steps, while facilitates subsequent protonation step *COOHNH toward formation. Impressively, CuPd –DAA assembled in flow cell presents highest Faradaic efficiency 72.1% yield rate 53.2 mmol h −1 g cat at −0.5 V versus RHE, representing nearly performance among all reported catalysts.

Язык: Английский

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Review on strategies for improving the added value and expanding the scope of CO₂ electroreduction products

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 5149 - 5189

Опубликована: Янв. 1, 2024

This review summarizes promising strategies including the design of catalysts and construction coupled electrocatalytic reaction systems, aimed at achieving selective production various products from CO 2 electroreduction.

Язык: Английский

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Microwave Quasi‐Solid State to Construct Strong Metal‐Support Interactions with Interfacial Electron‐Enriched Ru for Anion Exchange Membrane Electrolysis

Advanced Energy Materials, Год журнала: 2023, Номер 14(8)

Опубликована: Дек. 28, 2023

Abstract Regulating the metal‐support interaction of anchored metal nanoclusters is recognized as valid approach to optimize electrocatalytic performance through tuning interfacial electronic structure. However, developing novel support and understanding electron accumulation on modulating reaction kinetics are still elusive. Herein, highly‐dispersed Ruthenium (Ru) onto phosphorous doped molybdenum boride (Ru/P‐MoB) developed ultrafast microwave‐plasma (60 s) approach. The synthesized Ru/P‐MoB impressively promote hydrogen evolution with low overpotentials 34, 45, 40 mV drive 10 mA cm −2 in alkaline freshwater, seawater acid media. Specially, it presents superior turnover frequency mass/specific activity relative Pt/C, Ru/C, Ru/MoB. Moreover, anion exchange membrane (AEM) electrolyzer cell based can achieve 500 1000 small voltages 1.71 1.78 V good durability. Experimental density functional theoretical (DFT) analysis reveal that strong interactions (Ru─Mo Ru─P bonds) generated electron‐enriched Ru, then favoring water‐molecule adsorption/dissociation optimal H intermediate adsorption free energy. This work provides designing avenue exploit electrocatalysts outstanding catalytic under high current at practical high‐temperature.

Язык: Английский

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Efficient Electrochemical Co‐Reduction of Carbon Dioxide and Nitrate to Urea with High Faradaic Efficiency on Cobalt‐Based Dual‐Sites

Advanced Materials, Год журнала: 2024, Номер 36(25)

Опубликована: Апрель 2, 2024

Abstract Renewable electricity‐powered nitrate/carbon dioxide co‐reduction reaction toward urea production paves an attractive alternative to industrial processes and offers a clean on‐site approach closing the global nitrogen cycle. However, its large‐scale implantation is severely impeded by challenging C–N coupling requires electrocatalysts with high activity/selectivity. Here, cobalt‐nanoparticles anchored on carbon nanosheet (Co NPs@C) are proposed as catalyst electrode boost yield Faradaic efficiency (FE) electrosynthesis enhanced coupling. Such Co NPs@C renders superb urea‐producing activity FE reaching 54.3% of 2217.5 µg h −1 mg cat. , much superior NPs C counterparts, meanwhile shows strong stability. The affords rich catalytically active sites, fast reactant diffusion, sufficient catalytic surfaces‐electrolyte contacts favored charge ion transfer efficiencies. theoretical calculations reveal that high‐rate formation *CO *NH 2 intermediates crucial for facilitating synthesis.

Язык: Английский

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Electrocatalytic synthesis of C–N coupling compounds from CO₂ and nitrogenous species

SusMat, Год журнала: 2024, Номер 4(2)

Опубликована: Март 12, 2024

Abstract The electrocatalytic synthesis of C–N coupling compounds from CO 2 and nitrogenous species not only offers an effective avenue to achieve carbon neutrality reduce environmental pollution, but also establishes a route synthesize valuable chemicals, such as urea, amide, amine. This innovative approach expands the application range product categories beyond simple carbonaceous in reduction, which is becoming rapidly advancing field. review summarizes research progress urea synthesis, using N , NO − 3 species, explores emerging trends electrosynthesis amide amine nitrogen species. Additionally, future opportunities this field are highlighted, including amino acids other containing bonds, anodic reactions water oxidation, catalytic mechanism corresponding reactions. critical captures insights aimed at accelerating development electrochemical reactions, confirming superiority method over traditional techniques.

Язык: Английский

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Tandem Catalysts Enabling Efficient C−N Coupling toward the Electrosynthesis of Urea

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 6, 2024

Abstract The development of a methodology for synthesizing value‐added urea (CO(NH 2 ) via renewable electricity‐driven C−N coupling reaction under mild conditions is highly anticipated. However, the complex catalytic active sites that act on carbon and nitrogen species make mechanism unclear, resulting in low efficiency from co‐reduction dioxide (CO nitrate (NO 3 − ). Herein, we propose novel tandem catalyst Mo‐PCN‐222(Co), which Mo serve to facilitate reduction *NH intermediate, while Co enhance CO carbonic oxide (CO), thus synergistically promoting coupling. synthesized Mo‐PCN‐222(Co) exhibited noteworthy yield rate 844.11 mg h −1 g , alongside corresponding Faradaic 33.90 % at −0.4 V vs. reversible hydrogen electrode (RHE). By combining situ spectroscopic techniques with density functional theory calculations, demonstrate efficient attributed system *CO intermediates produced by stabilize formation *CONH intermediate. This study provides an effective avenue design synthesis catalysts electrocatalytic synthesis.

Язык: Английский

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Fundamentals and Rational Design of Heterogeneous C‐N Coupling Electrocatalysts for Urea Synthesis at Ambient Conditions

Advanced Energy Materials, Год журнала: 2024, Номер 14(28)

Опубликована: Янв. 28, 2024

Abstract Electrocatalytic C‐N coupling reaction is regarded as a promising strategy for achieving clean and sustainable urea production by coreducing CO 2 nitrogen species, thus contributing to carbon neutrality the artificial cycle. However, restricted sluggish adsorption of reactants, competitive side reactions, multistep pathways, electrochemical suffers from low yield rate selectivity so far. In order comprehensively improve synthesis performance, it crucial develop highly efficient catalysts coupling. this article, catalyst‐designing strategies, mechanisms, fundamental research methods are reviewed. For coreduction different several prevailing mechanisms discussed. With aim establishing standard system, fundamentals electrocatalytic introduced. The most important strategies boosting discussed, including heteroatom doping, vacancy engineering, crystal facet regulation, atom‐scale modulation, alloying heterostructure construction. Finally, challenges perspectives proposed future industrial applications

Язык: Английский

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Efficient Electrosynthesis of Urea over Single‐Atom Alloy with Electronic Metal Support Interaction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)

Опубликована: Май 24, 2024

Urea electrosynthesis from carbon dioxide (CO

Язык: Английский

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A Coherent Pd–Pd₁₆B₃ Core–Shell Electrocatalyst for Controlled Hydrogenation in Nitrogen Reduction Reaction

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

Опубликована: Март 7, 2024

Abstract The manipulation of surface catalytic sites has rarely been explored for metal borides, and the subsurface effects on electrocatalytic activity nitrogen reduction reaction (NRR) remain unknown. Herein, this work develops a core–shell nanoparticle catalyst with Pd core that ensures high electron transfer rates an 16 B 3 atomical shell possess tunable active regulating NRR. atomic structural evolution from to is investigated by precisely controlling atom diffusion, molecular rearrangement, d – sp orbital hybridization. Pd/Pd nanocrystals exhibit exceptional NRR performance NH Faradaic efficiency 30.8%, which superior those pristine (1.2%) B‐doped (4.8%) under identical conditions, yield rate 0.81 µmol h −1 cm −2 . This discovers could promote selectivity separating hydrogen proceeded hole bridge sites, provide excellent conductivity through regulated interactions. Consequently, controlled chemical ordering palladium boride surfaces provides insight into synthesis advanced electrocatalysts.

Язык: Английский

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