Breaking the Scaling Relationship in C−N Coupling via the Doping Effects for Efficient Urea Electrosynthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(24)

Опубликована: Апрель 10, 2024

Abstract Electrochemical C−N coupling reaction based on carbon dioxide and nitrate have been emerged as a new “green synthetic strategy” for the synthesis of urea, but catalytic efficiency is seriously restricted by inherent scaling relations adsorption energies active sites, improvement activity frequently accompanied decrease in selectivity. Herein, doping engineering strategy was proposed to break relationship intermediate binding minimize kinetic barrier coupling. A thus designed SrCo 0.39 Ru 0.61 O 3−δ catalyst achieves urea yield rate 1522 μg h −1 mg cat. faradic 34.1 % at −0.7 V versus reversible hydrogen electrode. series characterizations revealed that Co not only induces lattice distortion also creates rich oxygen vacancies (O ) SrRuO 3 . The weaken *CO *NH 2 intermediates sites respectively, strain effects over Co−Ru dual promoting occurrence two monomers instead selective hydrogenating form by‐products. This work presents an insight into molecular reactions towards via

Язык: Английский

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Electrocatalytic upgrading of nitrogenous wastes into value-added chemicals: A review

Materials Today, Год журнала: 2024, Номер 73, С. 208 - 259

Опубликована: Фев. 7, 2024

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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Expanding the Horizons of Machine Learning in Nanomaterials to Chiral Nanostructures

Advanced Materials, Год журнала: 2024, Номер 36(18)

Опубликована: Янв. 19, 2024

Abstract Machine learning holds significant research potential in the field of nanotechnology, enabling nanomaterial structure and property predictions, facilitating materials design discovery, reducing need for time‐consuming labor‐intensive experiments simulations. In contrast to their achiral counterparts, application machine chiral nanomaterials is still its infancy, with a limited number publications date. This despite great advance development new sustainable high values optical activity, circularly polarized luminescence, enantioselectivity, as well analysis structural chirality by electron microscopy. this review, an methods used studying provided, subsequently offering guidance on adapting extending work nanomaterials. An overview within framework synthesis–structure–property–application relationships presented insights how leverage study these highly complex are provided. Some key recent reviewed discussed Finally, review captures achievements, ongoing challenges, prospective outlook very important field.

Язык: Английский

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First-principles and machine-learning approaches for interpreting and predicting the properties of MXenes

npj 2D Materials and Applications, Год журнала: 2025, Номер 9(1)

Опубликована: Фев. 1, 2025

MXenes are a versatile family of 2D inorganic materials with applications in energy storage, shielding, sensing, and catalysis. This review highlights computational studies using density functional theory machine-learning approaches to explore their structure (stacking, functionalization, doping), properties (electronic, mechanical, magnetic), application potential. Key advances challenges critically examined, offering insights into applying research transition these from the lab practical use.

Язык: Английский

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Urea Electrosynthesis Accelerated by Theoretical Simulations

Advanced Functional Materials, Год журнала: 2023, Номер 34(14)

Опубликована: Дек. 27, 2023

Abstract Urea is not only a primary fertilizer in modern agriculture but also crucial raw material for the chemical industry. In past hundred years, prevailing industrial synthesis of urea heavily relies on Bosch–Meiser process to couple NH 3 and CO 2 under harsh conditions, resulting high carbon emissions energy consumption. The conversion carbon‐ nitrogen‐containing species into through electrochemical reactions ambient conditions represents sustainable strategy. Despite increasing reports electrosynthesis, comprehensive review that delves profound, atomic‐level comprehension fundamental reaction mechanisms currently absent. this Perspective, recent advancements from /CO various nitrogenous (i.e., N , NO x − NO) are presented, with special emphasis theoretical understanding C─N coupling mechanisms. Several key strategies facilitate then pinpointed, which enhance their applicability practical experiments highlight significant progress achieved field. At end, major obstacles potential opportunities advancing electrosynthesis accelerated by simulations situ techniques discussed. This hoped act as roadmap ignite fresh insights inspiration development electrocatalytic synthesis.

Язык: Английский

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A review on electrocatalytic CO₂ conversion via C–C and C–N coupling

Carbon Energy, Год журнала: 2024, Номер 6(2)

Опубликована: Фев. 1, 2024

Abstract Electrochemical C–C and C–N coupling reactions with the conversion of abundant inexpensive small molecules, such as CO 2 nitrogen‐containing species, are considered a promising route for increasing value reduction products. The development high‐performance catalysts is key to both electrocatalytic reactions. In this review, we present systematic summary reaction systems reduction, along mechanisms bonds over outstanding materials recently developed. intermediate species pathways related well catalyst‐structure relationship will be also discussed, aiming provide insights guidance designing efficient systems.

Язык: Английский

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Applications of doped-MXene-based materials for electrochemical energy storage

Coordination Chemistry Reviews, Год журнала: 2024, Номер 517, С. 216039 - 216039

Опубликована: Июнь 21, 2024

Язык: Английский

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Amino Acid Synthesis through C–N Coupling between α-Ketoacids and Hydroxylamine from Nitrate Reduction

ACS Catalysis, Год журнала: 2024, Номер 14(13), С. 10164 - 10171

Опубликована: Июнь 20, 2024

The artificial synthesis of amino acids is an important yet challenging subject. Electrocatalytic C–N coupling from organic and nitrogen sources provides opportunity for this target but with the difficulty bond formation toward production acids. Herein, we report (alanine, glutamic acid, glycine, leucine, valine) nitrate α-ketoacids a hybrid catalyst, cobalt phthalocyanine immobilized on carbon nanotubes (CoPc/CNT). Faradaic efficiency alanine CoPc/CNT as high 61%. CoPc catalyst integrated CNTs can catalyze reduction to hydroxylamine, which switched thermodynamically uphill downhill process. hydroxylamine intermediate attacks α-carbon α-ketoacid form oxime. Amino are produced by oximes catalyzed CNTs. bifunctionality steers tandem catalytic reaction efficient in one pot. This work identifies that enhancing key acid synthesis.

Язык: Английский

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Catalysis of C-N Coupling on High-Entropy Alloys

Journal of Catalysis, Год журнала: 2024, Номер 430, С. 115322 - 115322

Опубликована: Янв. 26, 2024

Catalyzing carbon–nitrogen (C-N) coupling using small abundant nitrogenous molecules is of growing interest to lessen the environmental impact industrial process. High-entropy alloys hold potential have surface sites optimized for each intermediates and by varying alloy composition catalyst it provides tunability adsorption energy distribution. We model C-N energies CO NO assume that *CO couples with an *NO-reduced intermediate. As more mechanistic inside needed, we limit coverage pairs *NO, providing a necessary but not sufficient condition catalytic activity. Two limiting cases simulating process are presented: one considering thermodynamic equilibrium out-of-equilibrium conditions. A Monte Carlo method connecting two limits suggested which reproduce trends observed in experiments. By partial pressure shape pair function space as well its optima altered. Our finds ternary AuCuPd optimum at equal CO/NO pressures copper be low pressures.

Язык: Английский

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