Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction

Chem, Год журнала: 2023, Номер 9(7), С. 1768 - 1827

Опубликована: Июнь 21, 2023

Язык: Английский

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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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Laser-controlled tandem catalytic sites of CuNi alloys with ampere-level electrocatalytic nitrate-to-ammonia reduction activities for Zn–nitrate batteries

Energy & Environmental Science, Год журнала: 2023, Номер 16(7), С. 2991 - 3001

Опубликована: Янв. 1, 2023

Laser-constructed CuNi alloy electrodes with tandem sites of Ni provide H* and Cu for NO 3 − reduction, achieving ampere-level reduction high-performance Zn–NO batteries.

Язык: Английский

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Thermally Enhanced Relay Electrocatalysis of Nitrate-to-Ammonia Reduction over Single-Atom-Alloy Oxides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7779 - 7790

Опубликована: Март 11, 2024

The electrochemical nitrate reduction reaction (NO3RR) holds promise for converting nitrogenous pollutants to valuable ammonia products. However, conventional electrocatalysis faces challenges in effectively driving the complex eight-electron and nine-proton transfer process of NO3RR while also competing with hydrogen evolution reaction. In this study, we present thermally enhanced nitrate-to-ammonia conversion over nickel-modified copper oxide single-atom alloy nanowires. catalyst demonstrates improved production performance a Faradaic efficiency approximately 80% yield rate 9.7 mg h–1 cm–2 at +0.1 V versus reversible electrode elevated cell temperatures. addition, system displays impressive stability, interference resistance, favorable energy consumption greenhouse gas emissions simulated industrial wastewater treatment. Complementary situ analyses confirm that significantly superior relay active species formed Ni sites facilitates thermal-field-coupled Cu surface-adsorbed *NOx hydrogenation. Theoretical calculations further support thermodynamic kinetic feasibility catalysis mechanism Ni1Cu model catalyst. This study introduces conceptual thermal-electrochemistry approach synergistic regulation catalytic processes, highlighting potential multifield-coupled advance sustainable-energy-powered chemical synthesis technologies.

Язык: Английский

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Modulating the Active Hydrogen Adsorption on Fe─N Interface for Boosted Electrocatalytic Nitrate Reduction with Ultra‐Long Stability

Advanced Materials, Год журнала: 2023, Номер 35(46)

Опубликована: Июль 25, 2023

The electrocatalytic reduction of nitrate (NO3- ) to nitrogen (N2 is an environmentally friendly approach for efficient N-cycle management (toward a nitrogen-neutral cycle). However, poor catalyst durability and the competitive hydrogen evolution reaction significantly impede its practical application. Interface-chemistry engineering, utilizing close relationship between surface/interface microenvironment electron/proton transfer process, has facilitated development catalysts with high intrinsic activity physicochemical durability. This study reports synthesis nitrogen-doped carbon-coated rice-like iron nitride (RL-Fe2 N@NC) electrocatalyst excellent nitrate-reduction (high N2 selectivity (≈96%) NO3- conversion (≈86%)). According detailed mechanistic investigations by in situ tests theoretical calculations, strong hydrogenation ability enhanced enrichment system synergistically contribute rapid nitrogen-containing species, increasing reducing occurrence competing hydrogen-evolution side reaction. Moreover, RL-Fe2 N@NC shows stability, retaining good -to-N2 electrocatalysis more than 40 cycles (one cycle per day). paper could guide interfacial design Fe-based composite nanostructures reduction, facilitating shift toward neutrality.

Язык: Английский

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Ammonia Electrosynthesis from Nitrate Using a Ruthenium–Copper Cocatalyst System: A Full Concentration Range Study

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 668 - 676

Опубликована: Дек. 28, 2023

Electrochemical synthesis of ammonia via the nitrate reduction reaction (NO3RR) has been intensively researched as an alternative to traditional Haber–Bosch process. Most research focuses on low concentration range representative level in wastewater, leaving high range, which exists nuclear and fertilizer wastes, unexplored. The use a concentrated electrolyte (≥1 M) for higher rate production is hampered by poor hydrogen transfer kinetics. Herein, we demonstrate that cocatalytic system Ru/Cu2O catalyst enables NO3RR at 10.0 A 1 M 16 cm2 flow electrolyzer, with 100% faradaic efficiency toward ammonia. Detailed mechanistic studies deuterium labeling operando Fourier transform infrared (FTIR) spectroscopy allow us probe intermediate species Ru/Cu2O. Ab initio molecular dynamics (AIMD) simulations reveal adsorbed hydroxide Ru nanoparticles increases density hydrogen-bonded water network near Cu2O surface, promotes rate. Our work highlights importance engineering synergistic interactions cocatalysts addressing kinetic bottleneck electrosynthesis.

Язык: Английский

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Highly Efficient Electrochemical Nitrate Reduction to Ammonia in Strong Acid Conditions with Fe₂M‐Trinuclear‐Cluster Metal–Organic Frameworks

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Май 10, 2023

Nitrate-containing industrial wastewater poses a serious threat to the global food security and public health safety. As compared traditional microbial denitrification, electrocatalytic nitrate reduction shows better sustainability with ultrahigh energy efficiency production of high-value ammonia (NH3 ). However, nitrate-containing from most processes, such as mining, metallurgy, petrochemical engineering, is generally acidic, which contradicts typical neutral/alkaline working conditions for both denitrifying bacteria state-of-the-art inorganic electrocatalysts, leading demand pre-neutralization problematic hydrogen evaluation reaction (HER) competition catalyst dissolution. Here, we report series Fe2 M (M=Fe, Co, Ni, Zn) trinuclear cluster metal-organic frameworks (MOFs) that enable highly efficient ammonium under strong acidic excellent stability. In pH=1 electrolyte, Co-MOF demonstrates NH3 yield rate 20653.5 μg h-1 mg-1site 90.55 % -Faradaic (FE), 98.5 -selectivity up 75 hr Additionally, successful in high-acidic directly produce sulfate nitrogen fertilizer, avoiding subsequent aqueous extraction preventing spillage loss. This cluster-based MOF structures provide new insights into design principles high-performance catalysts environmentally-relevant conditions.

Язык: Английский

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Intentional corrosion-induced reconstruction of defective NiFe layered double hydroxide boosts electrocatalytic nitrate reduction to ammonia

Nature Water, Год журнала: 2023, Номер 1(12), С. 1068 - 1078

Опубликована: Дек. 5, 2023

Язык: Английский

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Optimizing Intermediate Adsorption via Heteroatom Ensemble Effect over RuFe Bimetallic Alloy for Enhanced Nitrate Electroreduction to Ammonia

Advanced Energy Materials, Год журнала: 2023, Номер 13(31)

Опубликована: Июнь 30, 2023

Abstract The electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach for removal and NH synthesis at ambient conditions. As complex eight‐electron/nine‐proton transfer process, its performance relies heavily on the adsorption ability of intermediates catalyst surface, which determined by geometric electronic configurations active sites. In this work, heteroatom ensemble effect deliberately triggered over RuFe bimetallic alloy to optimize intermediate NO RR. A record‐high yield rate 118.8 mg h −1 high Faradaic efficiency 92.2% are achieved −1.4 V vs reversible hydrogen electrode, ranking top state‐of‐the‐art. Experimental computational results reveal that characteristics induced play crucial roles. Both Ru Fe display continuous state throughout Fermi level, suggesting electron density benefits whole result, facilitated − , efficient stabilization key intermediates, as well timely desorption simultaneously achieved, thus significantly promoting direct .

Язык: Английский

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Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 1, 2024

Abstract Nitrate can be electrochemically degraded to produce ammonia while treating sewage it remains grand challenge simultaneously realize high Faradaic efficiency and production rate over wide-range concentrations in real wastewater. Herein, we report the defect-rich Cu nanowire array electrode generated by in-situ electrochemical reduction, exhibiting superior performance nitrate reduction reaction benefitting from triple synergistic modulation. Notably, delivers current density ranging 50 1100 mA cm −2 across wide (1–100 mM) with 90%. Operando Synchrotron radiation Fourier Transform Infrared Spectroscopy theoretical calculations revealed that defective sites enhance adsorption, promote water dissociation suppress hydrogen evolution. A two-electrode system integrating industrial wastewater glycerol oxidation achieves of 550 at −1.4 V 99.9% selectivity conversion 100 h stability, demonstrating outstanding practicability.

Язык: Английский

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