Overcoming Electrostatic Interaction via Pulsed Electroreduction for Boosting the Electrocatalytic Urea Synthesis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 10, 2024

Abstract Electrocatalytic urea synthesis under ambient conditions offers a promising alternative strategy to the traditional energy‐intensive industry protocol. Limited by electrostatic interaction, reduction reaction of anions at cathode in electrocatalytic system is not easily achievable. Here, we propose novel overcome interaction via pulsed electroreduction. We found that reconstruction‐resistant CuSiO x nanotube, with abundant atomic Cu−O−Si interfacial sites, exhibits ultrastability electrosynthesis from nitrate and CO 2 . Under potential approach optimal operating conditions, interfaces achieve superior production rate (1606.1 μg h −1 mg cat. ) high selectivity (79.01 %) stability (the Faradaic efficiency retained 80 % even after testing), outperforming most reported catalysts. believe our will incite further investigation into electroreduction increasing substrate transport, which may guide design other energy conversion systems.

Language: Английский

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Interfacial Engineering of Bimetallic Ni/Co-MOFs with H-Substituted Graphdiyne for Ammonia Electrosynthesis from Nitrate

ACS Nano, Journal Year: 2023, Volume and Issue: 17(7), P. 6687 - 6697

Published: March 17, 2023

The electrochemical synthesis of ammonia is highly dependent on the coupling reaction between nitrate and water, for which an electrocatalyst with a multifunctional interface anticipated to promote deoxygenation hydrogenation water. Herein, by engineering surface bimetallic Ni/Co-MOFs (NiCoBDC) hydrogen-substituted graphdiyne (HsGDY), hybrid nanoarray NiCoBDC@HsGDY has been achieved toward scale-up nitrate-to-ammonia conversion. On one hand, partial electron transfers from Ni2+ coordinatively unsaturated Co2+ NiCoBDC, not only promotes *NO3 but also activates water-dissociation *H Ni2+. other conformal coated HsGDY facilitates both electrons NO3- ions gathering NiCoBDC HsGDY, moves forward rate-determining step *N *H2O Co2+. As result, such delivers high NH3 yield rates Faradaic efficiency above 90% over wide potential pH windows. When assembled into galvanic Zn-NO3- battery, power density 3.66 mW cm-2 achieved, suggesting its in area aqueous Zn-based batteries.

Language: Английский

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Recent Advances in Electrocatalytic Nitrate Reduction to Ammonia: Mechanism Insight and Catalyst Design

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(21), P. 7965 - 7985

Published: May 16, 2023

Excessive discharge of nitrate pollutants has caused an imbalance in the nitrogen cycle, which threatened human health and ecosystems. Clean electrocatalytic reduction technology can convert into high value-added ammonia to control water pollution, truly realizing "turning waste treasure". This review highlights latest mechanisms proposed by combining situ characterization discusses various intermediates produced during reaction process key steps that determine rate. Meanwhile, four common catalyst synthesis strategies are systematically summarized. These have exhibited preeminent results terms conductivity active sites inhibition side effects. Finally, challenges difficulty (NRA) development main direction future discussed. The engineering for increasing stability performance also aims provide guidance efficient conversion promotes advancement sustainable chemistry.

Language: Английский

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Activity and Selectivity Roadmap for C–N Electro-Coupling on MXenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15572 - 15580

Published: July 6, 2023

Electrochemical coupling between carbon and nitrogen species to generate high-value C-N products, including urea, presents significant economic environmental potentials for addressing the energy crisis. However, this electrocatalysis process still suffers from limited mechanism understanding due complex reaction networks, which restricts development of electrocatalysts beyond trial-and-error practices. In work, we aim improve mechanism. This goal was achieved by constructing activity selectivity landscape on 54 MXene surfaces density functional theory (DFT) calculations. Our results show that step is largely determined *CO adsorption strength (Ead-CO), while relies more co-adsorption *N (Ead-CO Ead-N). Based these findings, propose an ideal catalyst should satisfy moderate stable adsorption. Through machine learning-based approach, data-driven formulas describing relationship Ead-CO Ead-N with atomic physical chemistry features were further identified. identified formula, 162 materials screened without time-consuming DFT Several potential catalysts predicted good performance, such as Ta2W2C3. The candidate then verified study has incorporated learning methods first time provide efficient high-throughput screening method selective electrocatalysts, could be extended a wider range electrocatalytic reactions facilitate green chemical production.

Language: Английский

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Integrated Tandem Electrochemical‐chemical‐electrochemical Coupling of Biomass and Nitrate to Sustainable Alanine

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 18, 2023

Alanine is widely employed for synthesizing polymers, pharmaceuticals, and agrochemicals. Electrocatalytic coupling of biomass molecules waste nitrate attractive the removal alanine production under ambient conditions. However, reaction efficiency relatively low due to activation stable substrates, two reactive intermediates remains challenging. Herein, we realize integrated tandem electrochemical-chemical-electochemical synthesis from biomass-derived pyruvic acid (PA) (NO3- ) catalyzed by PdCu nano-bead-wires (PdCu NBWs). The overall pathway demonstrated as a multiple-step catalytic cascade process via NH2 OH PA on catalyst surface. Interestingly, in this electrochemical-chemical-electrochemical process, Cu facilitates electrochemical reduction intermediates, which chemically couple with form oxime, Pd promotes oxime desirable alanine. This work provides green strategy convert NO3- wealth enriches substrate scope renewable feedstocks produce high-value amino acids.

Language: Английский

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Spatial Management of CO Diffusion on Tandem Electrode Promotes NH₂ Intermediate Formation for Efficient Urea Electrosynthesis

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(8), P. 3373 - 3380

Published: July 14, 2023

Electrocatalytic urea synthesis is a promising alternative to the energy-intensive conventional industrial process. However, it lacks highly active and selective catalyst systems. Herein, we report Cu/ZnO stacked tandem gas-diffusion electrode (GDE) for from electrocatalytic CO2 nitrate reduction reactions. The ZnO layer (CL) segment at inlet provides high CO concentration downstream Cu CL segment, promoting conversion of NO3– *NH2. CO-mediated NH2 formation accelerates C–N coupling rate synthesis. As result, GDE with an optimal ZnO/Cu area ratio achieves Faradaic efficiency 37.4% yield 3.2 μmol h–1 cm–2 −0.3 V vs RHE under ambient conditions. This work expands application electrodes realizes cascade reaction.

Language: 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, Journal Year: 2023, Volume and Issue: 3(6), P. 781 - 820

Published: Dec. 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.

Language: Английский

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Synergistic electrocatalysis of crystal facet and O-vacancy for enhancive urea synthesis from nitrate and CO2

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 338, P. 122962 - 122962

Published: June 5, 2023

Language: Английский

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Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(14)

Published: Sept. 27, 2023

Hydrogenation reactions play a critical role in the synthesis of value-added products within chemical industry. Electrocatalytic hydrogenation (ECH) using water as hydrogen source has emerged an alternative to conventional thermocatalytic processes for sustainable and decentralized under mild conditions. Among various ECH catalysts, copper-based (Cu-based) nanomaterials are promising candidates due their earth-abundance, unique electronic structure, versatility, high activity/selectivity. Herein, recent advances application Cu-based catalysts upgrading valuable chemicals systematically analyzed. The properties initially introduced, followed by design strategies enhance activity selectivity. Then, typical on presented detail, including carbon dioxide reduction multicarbon generation, alkyne-to-alkene conversion, selective aldehyde ammonia production from nitrogen-containing substances, amine organic nitrogen compounds. In these catalyst composition nanostructures toward different is focused. co-hydrogenation two substrates (e.g., CO

Language: Английский

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

SusMat, Journal Year: 2024, Volume and Issue: 4(2)

Published: March 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.

Language: Английский

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