Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: June 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

Language: 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, Journal Year: 2023, Volume and Issue: 35(46)

Published: July 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.

Language: Английский

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Selective CO₂ Reduction to Ethylene Mediated by Adaptive Small‐molecule Engineering of Copper‐based Electrocatalysts

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Oct. 30, 2023

Electrochemical CO2 reduction reaction (CO2 RR) over Cu catalysts exhibits enormous potential for efficiently converting to ethylene (C2 H4 ). However, achieving high C2 selectivity remains a considerable challenge due the propensity of undergo structural reconstruction during RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating Cu-based material pathway facilitates products. An excellent Faraday efficiency (FE) 63.6 % on with current density 497.2 mA cm-2 flow cell was achieved, about 6.5 times higher than pristine catalyst which mainly produce CH4 . The X-ray absorption spectroscopy and Raman studies reveal hydroxyl group TA stabilizes Cuδ+ Furthermore, theoretical calculations demonstrate /Cu0 interfaces lower activation energy barrier *CO dimerization, species stabilize *COH intermediate via hydrogen bonding, thereby promoting production. Such engineering modulated electronic structure provides promising achieve highly selective value-added chemicals.

Language: Английский

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Review on strategies for improving the added value and expanding the scope of CO₂ electroreduction products

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 5149 - 5189

Published: Jan. 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.

Language: Английский

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Electrosynthesis of α‐Amino Acids from NO and other NO_x species over CoFe alloy‐decorated Self‐standing Carbon Fiber Membranes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 31, 2023

Abstract The conversion of industrial exhaust gases nitrogen oxides into high‐value products is significantly meaningful for global environment and human health. And green synthesis amino acids vital biomedical research sustainable development mankind. Herein, we demonstrate an innovative approach converting nitric oxide (NO) to a series α‐amino (over 13 kinds) through electrosynthesis with α‐keto over self‐standing carbon fiber membrane CoFe alloy. essential leucine exhibits high yield 115.4 μmol h −1 corresponding Faradaic efficiency 32.4 %, gram can be obtained within 24 hours in lab as well ultra‐long stability (>240 h) the catalyst, which could convert NO NH 2 OH rapidly attacking acid subsequent hydrogenation form acid. In addition, this method also suitable other sources including gaseous or liquidus 3 − . Therefore, work not only presents promising prospects from gas nitrate‐laden waste water products, but has significant implications synthetizing catalytic science.

Language: Английский

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Water‐Stable Fluorous Metal–Organic Frameworks with Open Metal Sites and Amine Groups for Efficient Urea Electrocatalytic Oxidation

Small, Journal Year: 2023, Volume and Issue: 19(43)

Published: June 27, 2023

Urea oxidation reaction (UOR) is one of the promising alternative anodic reactions to water that has attracted extensive attention in green hydrogen production. The application specifically designed electrocatalysts capable declining energy consumption and environmental consequences major challenges this field. Therefore, goal achieve a resistant, low-cost, environmentally friendly electrocatalyst. Herein, water-stable fluorinated Cu(II) metalorganic framework (MOF) {[Cu2 (L)(H2 O)2 ]·(5DMF)(4H2 O)}n (Cu-FMOF-NH2 ; H4 L = 3,5-bis(2,4-dicarboxylic acid)-4-(trifluoromethyl)aniline) developed utilizing an angular tetracarboxylic acid ligand incorporates both trifluoromethyl (-CF3 ) amine (-NH2 groups. tailored structure Cu-FMOF-NH2 where linkers are connected by fluoride bridges surrounded dicopper nodes reveals 4,24T1 topology. When employed as electrocatalyst, requires only 1.31 V versus reversible electrode (RHE) deliver 10 mA cm-2 current density 1.0 m KOH with 0.33 urea electrolyte delivered even higher (50 at 1.47 RHE. This performance superior several reported catalysts including commercial RuO2 catalyst overpotential 1.52 investigation opens new opportunities develop utilize pristine MOFs potential electrocatalyst for various catalytic reactions.

Language: Английский

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Rare earth oxide based electrocatalysts: synthesis, properties and applications

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 714 - 763

Published: Dec. 18, 2023

The synthesis, properties and applications of rare earth oxide based electrocatalysts in electrocatalysis reactions.

Language: Английский

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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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Oxygen Vacancies‐Rich Metal Oxide for Electrocatalytic Nitrogen Cycle

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 13, 2023

Abstract The development of industry and agriculture has been accompanied by an artificially imbalanced nitrogen cycle, which threatens human health ecological environments. Electrocatalytic systems have emerged as a sustainable way converting nitrogen‐containing molecules into high value‐added chemicals. However, the construction high‐performance electrocatalysts remains challenging. oxygen vacancy engineering strategy promoted more research efforts to explore structure‐activity relationship between catalytic activity vacancies. This review systematically summarizes recent vacancies‐rich metal oxides for electro‐catalyzing cycling systems, involving electrocatalytic nitrate reduction reaction, nitric oxide C─N coupling, urea oxidation reaction. First, methods characterization vacancies are summarized. Then, effect on is discussed in terms regulating electronic structures electrocatalysts, improving electroconductivity catalysts, lowing energy barrier, strengthening adsorption activation intermediate species. Finally, future directions cycle anticipated.

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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