Nano‐Single‐Atom Heterointerface Engineering for pH‐Universal Electrochemical Nitrate Reduction to Ammonia DOI
Jian Song,

Shengjie Qian,

Wenqiang Yang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 5, 2024

Abstract Nano‐single‐atom‐catalysts have the potential to combine respective advantages of both nano‐catalysts and single‐atom‐catalysts thus exhibit enhanced performance. Generally, separation active sites in space limits interaction between single atoms nanoparticles. Heterointerface engineering has break this limitation. Regretfully, studies on interface effect nanoparticles are rarely reported. Herein, an unprecedented nano‐single‐atom heterointerface composed Fe single‐atoms carbon‐shell‐coated FeP (Fe SAC/FeP@C) is demonstrated as efficient electrocatalyst for nitrate reduction process from alkaline acidic. Compared with typical nano‐single‐atom‐catalysts SAC/FePO 4 ) SAC), constructed SAC/FeP@C heterostructure exhibits dramatically nitrate‐to‐ammonia Especially acidic media, maxmium Faradaic efficiency ammonia (NH 3 can reach 95.6 ± 0.5%, a maximum NH yield 36.2 3.1 mg h −1 cat (pH = 1.2), which considerably higher than previously Density functional theory calculations situ spectroscopic investigations indicate that unique charge redistribution at interface, together optimized electronic structure single‐atoms, strengthens intermediate adsorption catalytic activity. This work provides feasible strategy designing heterointerfaces, well valuable insights into conversion under environmentally relevant wastewater conditions.

Language: Английский

Cu1‐Fe Dual Sites for Superior Neutral Ammonia Electrosynthesis from Nitrate DOI
Biao Zhou,

Linghao Yu,

Weixing Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 21, 2024

Abstract The electrochemical nitrate reduction reaction (NO 3 RR) is able to convert − ) into reusable ammonia (NH ), offering a green treatment and resource utilization strategy of wastewater synthesis. conversion NO NH undergoes water dissociation generate active hydrogen atoms nitrogen‐containing intermediates hydrogenation tandemly. two relay processes compete for the same sites, especially under pH‐neutral condition, resulting in suboptimal efficiency selectivity electrosynthesis from . Herein, we constructed Cu 1 ‐Fe dual‐site catalyst by anchoring single on amorphous iron oxide shell nanoscale zero‐valent (nZVI) RR, achieving an impressive removal 94.8 % 99.2 neutral pH concentration 50 mg L −1 −N conditions, greatly surpassing performance nZVI counterpart. This superior can be attributed synergistic effect enhanced adsorption Fe sites strengthened activation single‐atom decreasing energy barrier rate‐determining step *NO‐to‐*NOH. work develops novel fabricating catalysts enhance , presents environmentally sustainable approach treatment.

Language: Английский

Citations

36
General synthesis of high-entropy single-atom nanocages for electrosynthesis of ammonia from nitrate DOI Creative Commons
Sishuang Tang, Minghao Xie,

Saerom Yu

et al.

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

Published: Aug. 13, 2024

Given the growing emphasis on energy efficiency, environmental sustainability, and agricultural demand, there's a pressing need for decentralized scalable ammonia production. Converting nitrate ions electrochemically, which are commonly found in industrial wastewater polluted groundwater, into offers viable approach both treatment production yet limited by low producibility scalability. Here we report versatile solution-phase synthesis of high-entropy single-atom nanocages (HESA NCs) Fe other five metals-Co, Cu, Zn, Cd, In-are isolated via cyano-bridges coordinated with C N, respectively. Incorporating isolating metals matrix resulted Fe-C5 active sites minimized symmetry lattice as well facilitated water dissociation thus hydrogenation process. As result, Fe-HESA NCs exhibited high selectivity toward NH3 from electrocatalytic reduction Faradaic efficiency 93.4% while maintaining yield rate 81.4 mg h−1 mg−1. waste sources provides an effective method authors nanocage catalysts efficient nitrate-to-ammonia conversion.

Language: Английский

Citations

23
Enhancing Compatibility of Two‐Step Tandem Catalytic Nitrate Reduction to Ammonia Over P‐Cu/Co(OH)2 DOI

Qiuyu Yan,

Rundong Zhao, Lihong Yu

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 11, 2024

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO − NH involves multiple proton‐coupled electron transfer processes by‐products 2 , H etc.), making high selectivity challenge. Herein, two‐phase nanoflower P‐Cu/Co(OH) electrocatalyst consisting of P‐Cu clusters P‐Co(OH) nanosheets designed match two‐step tandem process ) more compatible, avoiding excessive accumulation optimizing whole reaction. Focusing on initial 2e process, inhibited * desorption Cu sites in gives rise appropriate released electrolyte. Subsequently, exhibits superior capacity for trapping transforming desorbed during latter 6e due thermodynamic advantage contributions active hydrogen. In 1 m KOH + 0.1 leads yield rate 42.63 mg h cm Faradaic efficiency 97.04% at −0.4 V versus reversible hydrogen electrode. Such well‐matched achieves remarkable synthesis performance perspective catalytic reaction, offering novel guideline design RR electrocatalysts.

Language: Английский

Citations

23
Modulating the Surface Concentration and Lifetime of Active Hydrogen in Cu-Based Layered Double Hydroxides for Electrocatalytic Nitrate Reduction to Ammonia DOI
Hongmei Li, S Li,

Renjun Guan

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12042 - 12050

Published: July 29, 2024

Strategies incorporating heterometals to introduce surface-active hydrogen (*H) have been extensively utilized enhance the electrocatalytic activity of Cu-based catalysts in nitrate reduction reaction (NitRR). However, a comprehensive understanding *H behavior and its specific impact on regulating NitRR pathway remains elusive, particularly quantitative manner. In this study, we prepared group layered double hydroxides (LDHs) as model with diverse concentrations lifetimes. Our findings reveal that LDHs is highly dependent species could be modulated by incorporated heterometallic sites. Specifically, conducted situ analysis different LDH using time-resolved scanning electrochemical microscopy. The surface concentration lifetime at various applied potentials were quantified, enabling us establish relationship between performance. Therefore, optimal performance was achieved CuNi-LDHs, exhibiting faradaic efficiency 94.6% yield rate 2.7 mg h–1 cm–2 because appropriate lifetime. Additionally, observe trend CuNi > CuCo Cu CuRu CuFe CuMg terms for NH3 production. These results suggest effectively utilizing stable produced catalyst, one would allow favorable performance, offering promising strategy other hydrogenation reactions.

Language: Английский

Citations

22
Hollow Square Ni-Doped Copper Oxide Catalyst Boosting Electrocatalytic Nitrate Reduction DOI
Yi Li, Jinshan Wei,

Hexing Lin

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1672 - 1683

Published: Jan. 16, 2025

The electrochemical nitrate reduction reaction to ammonia (NRA) is gaining increasing attention as an eco-friendly approach convert harmful pollutants into high-value product ammonia. NRA involves two critical rate-determining steps: hydrogenation of the *NO and *NOH intermediates. composite Ni Cu has been demonstrated exhibit synergistic catalytic effects; however, research on combination CuO remains limited. Herein, advanced Ni-doped copper oxide catalyst with a hollow square morphology (Ni–CuO) reported Faradaic efficiency 95.26% at −0.8 V vs RHE high yield rate 0.94 mmol h–1 cm–2, demonstrating selectivity stability. Complementary analyses that active hydrogen generated sites facilitates *NOx adsorbed sites. Theoretical computations further confirm thermodynamic viability this bimetallic mechanism. Furthermore, Al–NO3– battery open-circuit voltage was constructed by using Ni–CuO cathode. This work presents synergistically modulated for complex processes introduces highly efficient capable simultaneous NH3 synthesis electrical energy conversion, underscoring its potential in catalysis development chemical industries.

Language: Английский

Citations

6
Coupling Nitrate‐to‐Ammonia Conversion and Sulfion Oxidation Reaction Over Hierarchical Porous Spinel MFe2O4 (M═Ni, Co, Fe, Mn) in Wastewater DOI Open Access

Junyang Ding,

Lang Zhang, Zihao Wei

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

The construction of coupled electrolysis systems utilizing renewable energy sources for electrocatalytic nitrate reduction and sulfion oxidation reactions (NO3RR SOR), is considered a promising approach environmental remediation, ammonia production, sulfur recovery. Here, simple chemical dealloying method reported to fabricate hierarchical porous multi-metallic spinel MFe2O4 (M═Ni, Co, Fe, Mn) dual-functional electrocatalysts consisting Mn-doped NiFe2O4/CoFe2O4 heterostructure networks Ni/Co/Mn co-doped Fe3O4 nanosheet networks. excellent NO3RR with high NH3 Faradaic efficiency 95.2% at -0.80 V versus reversible hydrogen electrode (vs RHE) yield rate 608.9 µmol h-1 cm-2 -1.60 vs RHE, impressive SOR performance (100 mA [email protected] achieved MFe2O4. Key intermediates such as *NO, *NH2, are identified in the process by situ Fourier transform infrared spectroscopy (in FTIR). MFe2O4-assembled two-electrode coupling system (NO3RR||SOR) shows an ultra-low cell voltage 1.14 10 cm-2, much lower than NO3RR||OER (oxygen evolution reaction, [email protected] V), simultaneously achieving two expected targets value-added generation recovery, also demonstrating durability 18 h. This work demonstrates great potential ferrite-based catalysts remediation.

Language: Английский

Citations

3
A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction DOI Creative Commons

Jiacheng Jayden Wang,

Huong Thi Bui,

Xunlu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 8012 - 8023

Published: Feb. 18, 2025

The electrocatalytic nitrite reduction (NO2RR) converts nitrogen-containing pollutants to high-value ammonia (NH3) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead low activity NH3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper-zinc cyanamide (Cu0.8Zn0.2NCN) with localized structure distortion tailored surface electrostatic potential, allowing asymmetric binding of NO2-. It exhibits outstanding NO2RR performance Faradaic efficiency ∼100% an yield 22 mg h-1 cm-2, among best such process. Theoretical calculations in situ spectroscopic measurements demonstrate that Cu-Zn sites coordinated linear polarized [NCN]2- could transform symmetric [Cu-O-N-O-Cu] CuNCN-NO2- [Cu-N-O-Zn] configuration Cu0.8Zn0.2NCN-NO2-, thus enhancing adsorption bond cleavage. A paired electro-refinery Cu0.8Zn0.2NCN cathode reaches 2000 mA cm-2 at 2.36 V remains fully operational industrial-level 400 >140 h production rate ∼30 mgNH3 cm-2. Our work opens new avenue tailoring potentials using strategy advanced electrocatalysis.

Language: Английский

Citations

3
Subnanometric Nickel Phosphide Heteroclusters with Highly Active Niδ+–Pδ− Pairs for Nitrate Reduction toward Ammonia DOI
Qi Hu, Chunyan Shang, Xinbao Chen

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

The development of efficient electrocatalysts for the neutral nitrate reduction reaction (NO3–RR) toward ammonia (NH3) is essential to address environmental issues caused by NO3– but remains considerably challenging owing sluggish kinetics NO3–RR in media. Herein, we report subnanometric heteroclusters with strongly coupled nickel–phosphorus (Ni–P) dual-active sites as boost NO3–RR. Experimental and theoretical results reveal that feature Ni–P promotes electron transfer from Ni P, generating Niδ+–Pδ− active pairs, which Niδ+ species are highly Pδ− tunes interfacial water hydrogen bonding network promote dissociation step accelerate proton during Consequently, NO3–RR, exhibit a large NH3 yield rate 0.61 mmol h–1 cm–2 at −0.8 V versus reversible electrode, 2.8- 3.3-fold larger than those on nanoparticles clusters, respectively, generated exists NH4+ electrolytes. This study offers an approach boosting electrocatalytic reactions multiple intermediates designing sites.

Language: Английский

Citations

2
Unveiling Ionized Interfacial Water‐Induced Localized H* Enrichment for Electrocatalytic Nitrate Reduction DOI
Sujun Zheng, Xiaoyu Dong, Hong Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 4, 2024

Electrocatalytic nitrate reduction reaction (NO

Language: Английский

Citations

15
Bi1‐CuCo2O4 Hollow Carbon Nanofibers Boosts NH3 Production from Electrocatalytic Nitrate Reduction DOI

Hexing Lin,

Jinshan Wei, Ying Guo

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 6, 2024

Abstract Ammonia, as a high‐energy‐density carrier for hydrogen storage, is in great demand worldwide. Electrocatalytic nitrate reduction reaction (NO 3 RR) provides green NH production process. However, the complex pathways NO RR to and difficulty controlling intermediate products limit Herein, by incorporating atomic‐level bismuth (Bi) into CuCo 2 O 4 hollow carbon nanofibers, catalytic activity of electrocatalyst enhanced. The maximum Faradaic efficiency Bi 1 ‐CuCo 95.53%, with an yield 448.74 µmol h −1 cm −2 at −0.8 V versus RHE. Density Functional Theory calculations show that presence lowers barrier hydrogenation step from *NO H, while promoting mass transfer on release *NH reactivation surface‐active sites. Differential charge density also after doping, supplied catalyst − increases 0.62 0.72 e ‐ , thus reasoned enhanced activity. established nitrate‐Zn battery shows energy 2.81 mW implying potential application.

Language: Английский

Citations

12