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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Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application

Advanced Materials, Год журнала: 2023, Номер 35(31)

Опубликована: Фев. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Язык: Английский

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Electrochemical C–N coupling of CO₂and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds

Chemical Society Reviews, Год журнала: 2023, Номер 52(6), С. 2193 - 2237

Опубликована: Янв. 1, 2023

Electrochemical C–N coupling reaction by renewable electricity for the electrosynthesis of organonitrogen compounds with abundant CO 2 and nitrogenous small molecules as carbon nitrogen sources, respectively, is a promising sustainable synthetic strategy.

Язык: Английский

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Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июль 26, 2023

Electrocatalytic urea synthesis is an emerging alternative technology to the traditional energy-intensive industrial protocol. Novel strategies are urgently needed promote electrocatalytic C-N coupling process and inhibit side reactions. Here, we report a CuWO4 catalyst with native bimetallic sites that achieves high production rate (98.5 ± 3.2 μg h-1 mg-1cat) for co-reduction of CO2 NO3- Faradaic efficiency (70.1 2.4%) at -0.2 V versus reversible hydrogen electrode. Mechanistic studies demonstrated combination stable intermediates *NO2 *CO increases probability reduces potential barrier, resulting in low overpotential. This study provides new perspective on achieving efficient electrosynthesis by stabilizing key reaction intermediates, which may guide design other electrochemical systems high-value bond-containing chemicals.

Язык: Английский

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Selective electrochemical synthesis of urea from nitrate and CO2 via relay catalysis on hybrid catalysts

Nature Catalysis, Год журнала: 2023, Номер 6(10), С. 939 - 948

Опубликована: Сен. 11, 2023

Язык: Английский

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Construction of Catalytic Covalent Organic Frameworks with Redox‐Active Sites for the Oxygen Reduction and the Oxygen Evolution Reaction

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(49)

Опубликована: Окт. 14, 2022

Construction of catalytic covalent organic frameworks (COFs) for oxygen reduction reaction (ORR) and evolution (OER) is significant but rarely demonstrated. In this work, we have first constructed bifunctional COFs towards ORR OER by integrating diarylamine derivatives into the Co-porphyrin based frameworks. Both new (CoTAPP-PATA-COF CoTAPP-BDTA-COF) good ordered structures, high surface areas, robust chemical stability. The units, as a typical electron donor redox-active cores, promote intramolecular transport along improve electrochemically active areas. Thus, showed higher activities than that COF without units. CoTAPP-PATA-COF had halfwave potential 0.80 V ORR, delieved an overpotential 420 mV in 0.1 M KOH. theoretical calculation revealed introducing unites improved electrocatalysis.

Язык: Английский

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Electrochemical Upgrading of Formic Acid to Formamide via Coupling Nitrite Co-Reduction

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(35), С. 16006 - 16011

Опубликована: Июль 29, 2022

Formic acid (HCOOH) can be exclusively prepared through CO2 electroreduction at an industrial current density (0.5 A cm–2). However, the global annual demand for formic is only ∼1 million tons, far less than emission scale. The exploration of economical and green approach to upgrading CO2-derived significant. Here, we report electrochemical process convert nitrite into high-valued formamide over a copper catalyst under ambient conditions, which offers selectivity from up 90.0%. Isotope-labeled in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy quasi electron paramagnetic resonance results reveal key C–N bond formation coupling *CHO *NH2 intermediates. This work strategy upgrade high-value formamide.

Язык: Английский

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Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июль 28, 2023

Electrocatalytic reduction of waste nitrates (NO3-) enables the synthesis ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate high catalytic activity uniquely favor mono-nitrogen products. However, reaction fundamentals remain largely underexplored. Herein, we report set 14; 3d-, 4d-, 5d- f-block M-N-C catalysts. The selectivity NO3- to NH3 media, with specific focus on deciphering role NO2- intermediate cascade, reveals strong correlations (R=0.9) between for NH3. Moreover, theoretical computations reveal associative/dissociative adsorption pathways evolution, over normal M-N4 sites their oxo-form (O-M-N4) oxyphilic metals. This work provides platform designing multi-element NO3RR cascades single-atom or hybridization extended surfaces.

Язык: Английский

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Turning Waste into Wealth: Sustainable Production of High-Value-Added Chemicals from Catalytic Coupling of Carbon Dioxide and Nitrogenous Small Molecules

ACS Nano, Год журнала: 2022, Номер 16(11), С. 17911 - 17930

Опубликована: Окт. 31, 2022

Carbon neutrality is one of the central topics not only scientific community but also majority human society. The development highly efficient carbon dioxide (CO2) capture and utilization (CCU) techniques expected to stimulate routes concepts go beyond fossil fuels provide more economic benefits for a carbon-neutral economy. While various single-carbon (C1) multi-carbon (C2+) products have been selectively produced date, scope CCU can be further expanded valuable chemicals simple species by integration nitrogenous reactants into CO2 reduction. In this Review, research progress toward sustainable production high-value-added (urea, methylamine, ethylamine, formamide, acetamide, glycine) from catalytic coupling small molecules (NH3, N2, NO3–, NO2–) highlighted. C–N bond formation key mechanistic step in N-integrated reduction, so we focus on possible pathways starting reduction processes as well attributes that enable coupling. We propose directions prospects field, aiming inspire future investigations achieve comprehensive improvement performance product systems.

Язык: Английский

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Electrocatalytic Synthesis of Essential Amino Acids from Nitric Oxide Using Atomically Dispersed Fe on N‐doped Carbon

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 19, 2023

How to transfer industrial exhaust gases of nitrogen oxides into high-values product is significantly important and challenging. Herein, we demonstrate an innovative method for artificial synthesis essential α-amino acids from nitric oxide (NO) by reacting with α-keto through electrocatalytic process atomically dispersed Fe supported on N-doped carbon matrix (AD-Fe/NC) as the catalyst. A yield valine 32.1 μmol mgcat-1 delivered at -0.6 V vs. reversible hydrogen electrode, corresponding a selectivity 11.3 %. In situ X-ray absorption fine structure synchrotron radiation infrared spectroscopy analyses show that NO source converted hydroxylamine promptly nucleophilic attacked electrophilic center acid form oxime subsequent reductive hydrogenation occurred way amino acid. Over 6 kinds have been successfully synthesized gaseous can be also replaced liquid (NO3- ). Our findings not only provide creative converting high-valued products, which epoch-making significance towards acids, but benefit in deploying near-zero-emission technologies global environmental economic development.

Язык: Английский

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