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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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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Review on Electrocatalytic Coreduction of Carbon Dioxide and Nitrogenous Species for Urea Synthesis

ACS Nano, Год журнала: 2023, Номер 17(4), С. 3209 - 3224

Опубликована: Фев. 14, 2023

The electrochemical coreduction of carbon dioxide (CO2) and nitrogenous species (such as NO3–, NO2–, N2, NO) for urea synthesis under ambient conditions provides a promising solution to realize carbon/nitrogen neutrality mitigate environmental pollution. Although an increasing number studies have made some breakthroughs in synthesis, the unsatisfactory Faradaic efficiency, low yield rate, ambiguous C–N coupling reaction mechanisms remain major obstacles its large-scale applications. In this review, we present recent progress on based CO2 aqueous solutions conditions, providing useful guidance discussion rational design metal nanocatalyst, understanding mechanism, existing challenges prospects synthesis. We hope that review can stimulate more insights inspiration toward development electrocatalytic technology.

Язык: Английский

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Electrosynthesis of amino acids from NO and α-keto acids using two decoupled flow reactors

Nature Catalysis, Год журнала: 2023, Номер 6(10), С. 906 - 915

Опубликована: Авг. 21, 2023

Язык: Английский

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Electrosynthesis of formamide from methanol and ammonia under ambient conditions

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Сен. 16, 2022

Electrochemical conversion of abundant carbon- and nitrogen-containing small molecules into high-valued organonitrogen compounds is alluring to reducing current dependence on fossil energy. Here we report a single-cell electrochemical oxidation approach transform methanol ammonia formamide under ambient conditions over Pt electrocatalyst that provides 74.26% selectivity from Faradaic efficiency 40.39% at 100 mA cm

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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Efficient electrosynthesis of formamide from carbon monoxide and nitrite on a Ru-dispersed Cu nanocluster catalyst

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

Опубликована: Май 19, 2023

Conversion into high-value-added organic nitrogen compounds through electrochemical C-N coupling reactions under ambient conditions is regarded as a sustainable development strategy to achieve carbon neutrality and high-value utilization of harmful substances. Herein, we report an process for selective synthesis high-valued formamide from monoxide nitrite with Ru1Cu single-atom alloy conditions, which achieves high selectivity Faradaic efficiency 45.65 ± 0.76% at -0.5 V vs. RHE. In situ X-ray absorption spectroscopy, coupled in Raman spectroscopy density functional theory calculations results reveal that the adjacent Ru-Cu dual active sites can spontaneously couple *CO *NH2 intermediates realize critical reaction, enabling high-performance electrosynthesis formamide. This work offers insight electrocatalysis CO NO2- paving way more-sustainable chemical products.

Язык: Английский

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Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Accounts of Chemical Research, Год журнала: 2023, Номер 56(13), С. 1872 - 1883

Опубликована: Июнь 14, 2023

ConspectusThe hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic by using water (H2O) as hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid use high-pressure flammable gas or other toxic/expensive donors, which usually cause environmental, safety, cost concerns. Interestingly, utilizing easily available heavy (D2O) for deuterated syntheses also attractive due widespread applications molecules synthesis pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, how electrodes dictate outcomes remains elusive. Therefore, rational design nanostructured driving electrocatalytic series organics via H2O electrolysis developed.In this Account, we review recent advances different types functional groups, including C≡C, C≡N, C═C, C═O, C-Br/I bonds, -NO2, N-heterocycles, with over cathodes. First, general steps (reactant/intermediate adsorption, active atomic (H*) formation, surface reaction, product desorption) are analyzed, key factors proposed optimize performance (e.g., selectivity, activity, Faradaic efficiency (FE), rate, productivity) inhibit side reactions. Then, ex situ spectroscopic tools study intermediates interpret mechanisms introduced. Third, based knowledge mechanisms, introduce catalyst principles detail adoption reactants intermediates, promote formation H* from electrolysis, evolution reactions, improve FEs, space-time productivity products. We then some typical examples. (i) P- S-modified Pd decrease C═C adsorption enabling semihydrogenation alkynes high selectivity FEs at lower potentials. creating high-curvature nanotips concentrate substrates further speeds up process. (ii) By introducing low-coordination sites into Fe combining fluorine modify Co facilitate nitriles N-heterocycles activity obtained. (iii) forming isolated induce specific σ-alkynyl steering S vacancies Co3S4-x preferentially adsorb reduced group-decorated nitroarenes chemoselectivity realized. (iv) For reactant participated designing hydrophobic diffusion layer-supported ultrasmall Cu nanoparticles enhance mass transfer, activation, H2 ethylene ampere-level production 97.7% FE accomplished. Finally, provide outlook current challenges promising opportunities area. believe that summarized here paradigm highly selective nanomaterials achieve fascinating performances.

Язык: Английский

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Modulating Metal‐Nitrogen Coupling in Anti‐Perovskite Nitride via Cation Doping for Efficient Reduction of Nitrate to Ammonia

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Авг. 1, 2023

The complexes of metal center and nitrogen ligands are the most representative systems for catalyzing hydrogenation reactions in small molecule conversion. Developing heterogeneous catalysts with similar active metal-nitrogen functional centers, nevertheless, still remains challenging. In this work, we demonstrate that coupling anti-perovskite Co4 N can be effective modulated by Cu doping to form Co3 CuN, leading strongly promoted process during electrochemical reduction nitrate (NO3- RR) ammonia. combination advanced spectroscopic techniques density theory calculations reveal dopants strengthen Co-N bond upshifted d-band towards Fermi level, promoting adsorption NO3- *H facilitating transition from *NO2 /*NO H/*NOH. Consequently, CuN delivers noticeably better RR activity than pristine N, optimal Faradaic efficiency 97 % ammonia yield 455.3 mmol h-1 cm-2 at -0.3 V vs. RHE. This work provides an strategy developing high-performance catalyst synthesis.

Язык: Английский

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Toward effective electrocatalytic C–N coupling for the synthesis of organic nitrogenous compounds using CO₂ and biomass as carbon sources

SusMat, Год журнала: 2023, Номер 3(6), С. 781 - 820

Опубликована: Дек. 1, 2023

Abstract Thermochemical conversion of fossil resources into fuels, chemicals, and materials has rapidly increased atmospheric CO 2 levels, hindering global efforts toward achieving carbon neutrality. With the increasing push for sustainability, utilizing electrochemical technology to transform or biomass value‐added chemicals close cycle with sustainable energy sources represents a promising strategy. Expanding scope electrosynthesis is prerequisite electrification chemical manufacturing. To this end, constructing C─N bond considered priority. However, systematic review electrocatalytic processes building bonds using as not available. Accordingly, highlights research progress in organic nitrogen compounds from by coupling reactions view catalytic materials, focusing on enlightenment traditional catalysis understanding basis coupling. The possibility electrocatalysis also examined standpoints activation substrates, site, mechanism, inhibition hydrogen evolution reaction (HER). Finally, challenges prospects improved efficiency selectivity future development are discussed.

Язык: Английский

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