Cu–Fe Synergistic Active Sites Boost Kinetics of Electrochemical Nitrate Reduction DOI
Yilong Hua, Nan Song, Ziyang Wu

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(21)

Published: Jan. 31, 2024

Abstract Electrochemical conversion of nitrate offers an efficient solution to pollution and a sustainable strategy for ammonia generation. Cu Fe bimetallic electrocatalysts exhibit excellent electrochemical reduction (NO 3 RR) reactivity but the conventional preparation is complex time‐consuming this reaction still suffers from unsatisfied kinetic unidentified mechanisms. Herein, in situ electrodeposition employed induce modify active sites iron‐based N‐doping carbon nanofiber electrode (Fe/Fe C@NCNFs) during NO RR Cu‐contained solution. Benefiting synergistic effect between Cu─Fe/Fe C@NCNFs electrode, superior activity rate‐determining (*NO *NO 2 ) reduced energy barriers following deoxidation hydrogenation steps are achieved. Compared with Fe/Fe C@NCNFs‐500, pseudo‐first‐order (PFO) rate constant by demonstrates nearly two‐fold improvement high current efficiencies over wide pH voltage range. Furthermore, maximum ─N removal capacity N selectivity reach 15593.8 mg g −1 ca. 92% after twenty cycles. This work avenue highly design, paving more insights into interactions site construction performance.

Language: Английский

Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond DOI
Yuecheng Xiong, Yunhao Wang, Jingwen Zhou

et al.

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

Citations

214
Intermetallic Single-Atom Alloy In–Pd Bimetallene for Neutral Electrosynthesis of Ammonia from Nitrate DOI
Minghao Xie, Sishuang Tang, Li Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(25), P. 13957 - 13967

Published: June 19, 2023

Harvesting recyclable ammonia (NH3) from the electrocatalytic reduction of nitrate (NO3RR) offers a sustainable strategy to close ecological nitrogen cycle nitration contamination in an energy-efficient and environmentally friendly manner. The emerging intermetallic single-atom alloys (ISAAs) are recognized achieve highest site density single atoms by isolating contiguous metal into sites stabilized another within structure, which holds promise couple catalytic benefits nanocrystals catalysts for promoting NO3RR. Herein, ISAA In-Pd bimetallene, Pd isolated surrounding In atoms, is reported boost neutral NO3RR with NH3 Faradaic efficiency (FE) 87.2%, yield rate 28.06 mg h-1 mgPd-1, exceptional stability increased activity/selectivity over 100 h 20 cycles. structure induces substantially diminished overlap d-orbitals narrowed p-d hybridization In-p Pd-d states around Fermi level, resulting stronger NO3- adsorption depressed energy barrier potential-determining step Further integrating catalyst Zn-NO3- flow battery as cathode delivers power 12.64 mW cm-2 FE 93.4% production.

Language: Английский

Citations

167
Unveiling Cutting‐Edge Developments in Electrocatalytic Nitrate‐to‐Ammonia Conversion DOI
Haoran Zhang, Haijian Wang, X. P. Cao

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(16)

Published: Jan. 11, 2024

The excessive enrichment of nitrate in the environment can be converted into ammonia (NH

Language: Английский

Citations

166
Laser-controlled tandem catalytic sites of CuNi alloys with ampere-level electrocatalytic nitrate-to-ammonia reduction activities for Zn–nitrate batteries DOI

Wanqiang Yu,

Jiayuan Yu, Man Huang

et al.

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(7), P. 2991 - 3001

Published: Jan. 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.

Language: Английский

Citations

118
Atomic coordination environment engineering of bimetallic alloy nanostructures for efficient ammonia electrosynthesis from nitrate DOI Creative Commons
Yunhao Wang, Mingzi Sun, Jingwen Zhou

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(32)

Published: July 31, 2023

Electrochemical nitrate reduction reaction (NO 3 RR) to ammonia has been regarded as a promising strategy balance the global nitrogen cycle. However, it still suffers from poor Faradaic efficiency (FE) and limited yield rate for production on heterogeneous electrocatalysts, especially in neutral solutions. Herein, we report one-pot synthesis of ultrathin nanosheet-assembled RuFe nanoflowers with low-coordinated Ru sites enhance NO RR performances electrolyte. Significantly, exhibit outstanding FE 92.9% 38.68 mg h −1 cat (64.47 ) at −0.30 −0.65 V (vs. reversible hydrogen electrode), respectively. Experimental studies theoretical calculations reveal that are highly electroactive an increased d-band center guarantee efficient electron transfer, leading low energy barriers reduction. The demonstration rechargeable zinc-nitrate batteries large-specific capacity using indicates their great potential next-generation electrochemical systems.

Language: Английский

Citations

104
Sustainable conversion of alkaline nitrate to ammonia at activities greater than 2 A cm−2 DOI Creative Commons
Wanru Liao, Jun Wang,

Ganghai Ni

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 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.

Language: Английский

Citations

78
Sustainable Ammonia Electrosynthesis from Nitrate Wastewater Coupled to Electrocatalytic Upcycling of Polyethylene Terephthalate Plastic Waste DOI

Tianlun Ren,

Zuan Yu,

Hongjie Yu

et al.

ACS Nano, Journal Year: 2023, Volume and Issue: 17(13), P. 12422 - 12432

Published: June 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.

Language: Английский

Citations

73
Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia DOI Creative Commons
Yunhao Wang,

Fengkun Hao,

Mingzi Sun

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(14)

Published: Jan. 26, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) toward ammonia synthesis is recognized as a sustainable strategy to balance the global nitrogen cycle. However, it still remains great challenge achieve highly efficient production due complex proton‐coupled electron transfer process in NO RR. Here, controlled of RuMo alloy nanoflowers (NFs) with unconventional face‐centered cubic (fcc) phase and hexagonal close‐packed/fcc heterophase for RR reported. Significantly, fcc NFs demonstrate high Faradaic efficiency 95.2% large yield rate 32.7 mg h −1 cat at 0 −0.1 V (vs reversible hydrogen electrode), respectively. In situ characterizations theoretical calculations have unraveled that possess highest d‐band center superior electroactivity, which originates from strong Ru─Mo interactions intrinsic activity phase. The optimal electronic structures supply adsorption key intermediates suppression competitive evolution, further determines remarkable performance. successful demonstration high‐performance zinc‐nitrate batteries suggests their substantial application potential electrochemical energy systems.

Language: Английский

Citations

73
Unveiling the Reaction Mechanism of Nitrate Reduction to Ammonia Over Cobalt-Based Electrocatalysts DOI

Kaiwen Yang,

Shuhe Han, Chuanqi Cheng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 12976 - 12983

Published: April 3, 2024

Electrocatalytic reduction of nitrate to ammonia (NRA) has emerged as an alternative strategy for sewage treatment and generation. Despite excellent performances having been achieved over cobalt-based electrocatalysts, the reaction mechanism well veritable active species across a wide potential range are still full controversy. Here, we adopt CoP, Co, Co3O4 model materials solve these issues. CoP evolves into core@shell structured CoP@Co before NRA. For Co catalysts, three-step relay is carried out superficial dynamical Coδ+ under low overpotential, while continuous hydrogenation from unveiled high overpotential. In comparison, stable steadily catalyze range. As result, exhibit much higher NRA activity than especially Moreover, performance although they experience same mechanism. A series characterizations clarify reason enhancement highlighting that core donates abundant electrons species, leading generation more hydrogen nitrogen-containing intermediates.

Language: Английский

Citations

73
Electrochemical Co-Production of Ammonia and Biodegradable Polymer Monomer Glycolic Acid via the Co-Electrolysis of Nitrate Wastewater and Waste Plastic DOI

Tianlun Ren,

Zhongyao Duan,

Huizhen Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(15), P. 10394 - 10404

Published: July 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.

Language: Английский

Citations

59