Sustainable conversion of alkaline nitrate to ammonia at activities greater than 2 A cm−2

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

Опубликована: Фев. 10, 2024

Abstract Nitrate (NO 3 ‒ ) pollution poses significant threats to water quality and global nitrogen cycles. Alkaline electrocatalytic NO reduction reaction RR) emerges as an attractive route for enabling removal sustainable ammonia (NH synthesis. However, it suffers from insufficient proton (H + supply in high pH conditions, restricting -to-NH activity. Herein, we propose a halogen-mediated H feeding strategy enhance the alkaline RR performance. Our platform achieves near-100% NH Faradaic efficiency (pH = 14) with current density of 2 A cm –2 enables over 99% – conversion efficiency. We also convert high-purity 4 Cl near-unity efficiency, suggesting practical approach valorizing pollutants into valuable products. Theoretical simulations situ experiments reveal that Cl-coordination endows shifted d -band center Pd atoms construct local -abundant environments, through arousing dangling O-H dissociation fast *H desorption, *NO intermediate hydrogenation finally effective conversion.

Язык: Английский

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Sustainable Ammonia Electrosynthesis from Nitrate Wastewater Coupled to Electrocatalytic Upcycling of Polyethylene Terephthalate Plastic Waste

ACS Nano, Год журнала: 2023, Номер 17(13), С. 12422 - 12432

Опубликована: Июнь 26, 2023

Integrating the nitrate reduction reaction (NO3RR) with polyethylene terephthalate (PET) hydrolysate oxidation to construct nitrate/PET coelectrolysis system holds a great promise of realizing simultaneous upcycling wastewater and PET plastic waste, which, however, is still an almost untouched research area. Herein, we develop ultralow content Ru-incorporated Co-based metal-organic frameworks as bifunctional precatalyst, which can be in situ reconstructed Ru-Co(OH)2 at cathode Ru-CoOOH anode under electrocatalytic environments, function real active catalysts for NO3RR oxidation, respectively. With two-electrode system, current density 50 mA cm-2 achieved cell voltage only 1.53 V, production ammonia formate lower energy consumption. This study provides concept construction systems waste.

Язык: Английский

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Interfacial engineering of CoMn2O4/NC induced electronic delocalization boosts electrocatalytic nitrogen oxyanions reduction to ammonia

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 322, С. 122090 - 122090

Опубликована: Окт. 21, 2022

Язык: Английский

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Efficient tandem electroreduction of nitrate into ammonia through coupling Cu single atoms with adjacent Co3O4

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

Опубликована: Апрель 29, 2024

Abstract The nitrate (NO 3 − ) electroreduction into ammonia (NH represents a promising approach for sustainable NH synthesis. However, the variation of adsorption configurations renders great difficulties in simultaneous optimization binding energy intermediates. Though extensively reported Cu-based electrocatalysts benefit NO adsorption, one key issues lies accumulation nitrite 2 due to its weak resulting rapid deactivation catalysts and sluggish kinetics subsequent hydrogenation steps. Here we report tandem electrocatalyst by combining Cu single atoms with adjacent Co O 4 nanosheets boost . obtained catalyst exhibits yield rate 114.0 mg $${}_{{{{{{\rm{NH}}}}}}_3}$$ NH 3 h −1 cm −2 , which exceeds previous values catalysts. Mechanism investigations unveil that combination regulates configuration strengthens thus accelerating

Язык: Английский

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Intermediates Regulation via Electron‐Deficient Cu Sites for Selective Nitrate‐to‐Ammonia Electroreduction

Advanced Materials, Год журнала: 2023, Номер 35(48)

Опубликована: Сен. 21, 2023

Ammonia (NH3 ), known as one of the fundamental raw materials for manufacturing commodities such chemical fertilizers, dyes, ammunitions, pharmaceuticals, and textiles, exhibits a high hydrogen storage capacity ≈17.75%. Electrochemical nitrate reduction (NO3 RR) to valuable ammonia at ambient conditions is promising strategy facilitate artificial nitrogen cycle. Herein, copper-doped cobalt selenide nanosheets with selenium vacancies are reported robust highly efficient electrocatalyst ammonia, exhibiting maximum Faradaic efficiency ≈93.5% an yield rate 2360 µg h-1 cm-2 -0.60 V versus reversible electrode. The in situ spectroscopical theoretical study demonstrates that incorporation Cu dopants Se into efficiently enhances electron transfer from Co atoms via bridging atoms, forming electron-deficient structure sites accelerate NO3- dissociation stabilize *NO2 intermediates, eventually achieving selective catalysis entire NO3 RR process produce efficiently.

Язык: Английский

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

ACS Sustainable Chemistry & Engineering, Год журнала: 2023, Номер 11(21), С. 7965 - 7985

Опубликована: Май 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.

Язык: Английский

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Electrochemical Co-Production of Ammonia and Biodegradable Polymer Monomer Glycolic Acid via the Co-Electrolysis of Nitrate Wastewater and Waste Plastic

ACS Catalysis, Год журнала: 2023, Номер 13(15), С. 10394 - 10404

Опубликована: Июль 25, 2023

Electrochemical reformation of nitrate wastewater and poly(ethylene terephthalate) (PET) plastic waste into ammonia (NH3) fine chemicals is a sustainable strategy for resource utilization. Herein, co-production system glycolic acid (GA, degradable polymer monomer) constructed by coupling reduction ethylene glycol (EG, in PET hydrolysate) oxidation. Low-crystalline CoOOH (LC-CoOOH/CF) Pd nanothorns (Pd NTs/NF) grown situ on the metal foam substrates are employed as cathode anode, respectively. The high density amorphous regions LC-CoOOH/CF enables enhanced adsorption provides abundant active sites, ultimately leading to an Faradic efficiency (FE) 97.38 ± 1.0% at −0.25 V vs reversible hydrogen electrode (RHE). Meanwhile, unique nanothorn morphology endows NTs/NF with high-curvature tip, triggering tip effect (TE) promote highly selective oxidation EG GA. Furthermore, two-electrode system, NH3 GA operated low energy consumption (onset voltage: 0.5 V), much lower than traditional electrolysis process (1.4 V). This study method utilization co-produce value-added chemicals.

Язык: Английский

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Strategies and applications of electrocatalytic nitrate reduction towards ammonia

Coordination Chemistry Reviews, Год журнала: 2024, Номер 506, С. 215723 - 215723

Опубликована: Фев. 26, 2024

Язык: Английский

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Enhanced Nitrate‐to‐Ammonia Efficiency over Linear Assemblies of Copper‐Cobalt Nanophases Stabilized by Redox Polymers

Advanced Materials, Год журнала: 2023, Номер 35(32)

Опубликована: Май 26, 2023

Renewable electricity-powered nitrate (NO3- ) reduction reaction (NO3 RR) offers a net-zero carbon route to the realization of high ammonia (NH3 productivity. However, this suffers from low energy efficiency (EE, with half-cell EE commonly <36%), since overpotentials are required overcome weak NO3- binding affinity and sluggish NO3 RR kinetics. To alleviate this, rational catalyst design strategy that involves linear assembly sub-5 nm Cu/Co nanophases into sub-20 thick nanoribbons is suggested. The theoretical experimental studies show Cu-Co nanoribbons, similar enzymes, enable strong adsorption rapid tandem catalysis NH3 , owing their richly exposed binary phase boundaries adjacent sites at distance. In situ Raman spectroscopy further reveals applied overpotentials, rapidly activated subsequently stabilized by specifically designed redox polymer in scavenges intermediately formed highly oxidative nitrogen dioxide (NO2 ). As result, stable current density ≈450 mA cm-2 achieved, Faradaic >97% for formation an unprecedented ≈42%.

Язык: Английский

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Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

Advanced Materials, Год журнала: 2023, Номер 36(14)

Опубликована: Сен. 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

Язык: Английский

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