Modulation of the Second-Beyond Coordination Structure in Single-Atom Electrocatalysts for Confirmed Promotion of Ammonia Synthesis DOI
Qinglin Li, Lin Luo, Xiangyang Guo

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 147(2), P. 1884 - 1892

Published: Dec. 30, 2024

Although microenvironments surrounding single-atom catalysts (SACs) have been widely demonstrated to a remarkable effect on their catalytic performances, it remains unclear whether the local structure beyond secondary coordination shells works as well or not. Herein, we employed series of metal-organic frameworks (MOFs) with well-defined and tunable second-beyond spheres model SAC electrocatalysts discuss influence long-distance ammonia synthesis from nitrate, which were synthesized denoted Cu12-NDI-X (X = NMe2, H, F). It is first experimentally confirmed that remote substitution function groups sphere can remarkably affect activity synthesis. Meanwhile, -H endowed Cu12-NND-H exhibits superior yield (35.1 mg·h-1·mgcat-1) FE (98.7%) those modified -NMe2 -F, also shows good stability at 100 mA·cm-2. The promotion modulated unraveled result adjustable d-band center Cu active site leading promoted adsorption NO3- protonation key intermediates. Encouraged by its extraordinary yield, electrode cathode assemble one rechargeable Zn-nitrate battery an impressive power density 34.0 mW·cm-2, demonstrating promising application in energy conversion storage.

Language: Английский

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
Isolating Cu-Zn active-sites in Ordered Intermetallics to Enhance Nitrite-to-Ammonia Electroreduction DOI Creative Commons
Jiao Lan, Zhen Wang, Cheng‐Wei Kao

et al.

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

Published: Nov. 23, 2024

Electrocatalytic nitrite reduction to the valuable ammonia is a green and sustainable alternative conventional Haber-Bosch method for synthesis, while activity selectivity production remains poor at low concentrations. Herein, we report nanoporous intermetallic single-atom alloy CuZn (np/ISAA-CuZn) catalyst with completely isolated Cu-Zn active-sites, which achieves neutral reaction remarkable NH3 Faradaic efficiency over 95% highest energy of ≈ 59.1% in wide potential range from −0.2 −0.8 V vs. RHE. The np/ISAA-CuZn electrocatalyst was able operate stably 500 mA cm−2 220 h under membrane electrode assembly conditions stabilized Faraday ~80% high NO2‒ removal rate ~100%. A series situ experimental studies combined density functional theory calculations reveal that strong electronic interactions active-sites altered protonation adsorption species, effectively alleviating barrier *NO2 thus greatly facilitating selective NO2− into NH3. process, but its inefficient levels. Here authors an single atom stability concentration 1−10 mM.

Language: Английский

Citations

10
Relations between Structure, Composition, and Selectivity in Electrocatalytic Reduction of Nitrate-ions DOI Creative Commons
Yixiao Zhang,

Qingdian Liao,

Elena L. Gubanova

et al.

Current Opinion in Electrochemistry, Journal Year: 2025, Volume and Issue: 50, P. 101643 - 101643

Published: Jan. 10, 2025

Language: Английский

Citations

1
Enhancing Electrocatalytic Activity Through Targeted Local Electrolyte Micro‐Environment DOI Open Access
Yaping Yan, Min‐Hsien Wu, Le Zhou

et al.

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract The local electrolyte micro‐environment surrounding the catalyst reaction center, including critical factors such as pH, reactant concentration, and electric field, plays a decisive role in electrocatalytic reactions water splitting. Recently, this topic has garnered significant attention due to its potential significantly enhance catalytic performance. While various strategies optimize processes have been explored, deliberate control over fundamental principles guiding these adjustments remain their early stages of development. This review provides comprehensive examination key efforts aimed at designing tailoring localized micro‐environments improve It discusses advances micro‐environmental design, methodologies for evaluating shifts, mechanistic insights driving developments. Additionally, highlights existing challenges prospective industrial applications strategies. By offering detailed analysis recent developments, aims equip researchers with practical knowledge on controlling micro‐environments, thereby accelerating progress toward real‐world processes.

Language: Английский

Citations

1
Highly Efficient Electrocatalytic Nitrate Reduction to Ammonia: Group VIII-Based Catalysts DOI

Shiyue Yin,

Zhixi Guan,

Yuchuan Zhu

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 4, 2024

The accumulation of nitrates in the environment causes serious health and environmental problems. electrochemical nitrate reduction reaction (e-NO

Language: Английский

Citations

8
NH3 Synthesis from N1 Compounds by Photocatalytic Technology: Promotion Mechanism, Reaction Pathways, and Efficiency Evaluation Criteria DOI
Chunling Zhang, Jieyuan Li, Ruimin Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15721 - 15742

Published: Oct. 9, 2024

Ammonia (NH3) is one of the most important chemicals in high demand human society. Given high-energy consumption and environmental impact associated with Haber–Bosch process, an environmentally friendly method for NH3 synthesis under ambient conditions should be developed. The reduction N1 compounds, including nitrate (NO3–), nitrite (NO2–), nitric oxide (NOx), are more energetically favorable than that nitrogen (N2), avoiding activation inert N≡N bonds. Photocatalytic from compounds' reduction, which utilizes sunlight to convert contaminants into value-added chemicals, offers intriguing approach synthesis. This review a comprehensive overview progress research photocatalysis technology compounds Insight efficiency promotion mechanism provided, particularly focusing on optimization photocatalyst, mass transfer reactants, redox synergistic promotion. Moreover, reaction pathways summarized. evaluation criteria, accurate quantification yield, performance indicators, separation recovery, discussed guide systematic reliable Finally, current achievements future challenges photocatalytic critically discussed.

Language: Английский

Citations

6
Transition Metal‐Gallium Intermetallic Compounds with Tailored Active Site Configurations for Electrochemical Ammonia Synthesis DOI Creative Commons

Huaifang Zhang,

Chaoqun Ma,

Yichi Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(49)

Published: Sept. 4, 2024

Abstract Gallium (Ga) with a low melting point can serve as unique metallic solvent in the synthesis of intermetallic compounds (IMCs). The negative formation enthalpy transition metal‐Ga IMCs endows them high catalytic stability. Meanwhile, their tunable crystal structures offer possibility to tailor configurations active sites meet requirements for specific applications. Herein, we present general method preparing range IMCs, including Co−Ga, Ni−Ga, Pt−Ga, Pd−Ga, and Rh−Ga IMCs. structurally ordered CoGa body‐centered cubic ( bcc ) structure are uniformly dispersed on nitrogen‐doped reduced graphene oxide substrate (O‐CoGa/NG) deliver outstanding nitrate reduction reaction (NO 3 RR) performance, making excellent catalysts construct highly efficient rechargeable Zn‐NO − battery. Operando studies theoretical simulations demonstrate that electron‐rich environments around Co atoms enhance adsorption strength *NO intermediate simultaneously suppress hydrogen, thus improving NO RR activity selectivity.

Language: Английский

Citations

5
Covalent organic frameworks supported geminal-atom catalysts for upcycling nitrate into single-cell protein DOI

Jingdong Feng,

Wenda Zhang, Han Zhao

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160681 - 160681

Published: Feb. 1, 2025

Language: Английский

Citations

0
Maximizing Available Active Hydrogen on FeNi Substitutional Solid-Solution Alloy to Boost Electrosynthesis of Ammonia from Nitrate DOI
Xing Sun, Yanzheng He, Mengfan Wang

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

Electrochemical nitrate reduction reaction (NO3RR) stands out as a promising route for sustainable ammonia synthesis, in which active hydrogen (*H) plays crucial role both the deoxygenation and hydrogenation steps. However, regulation of surface *H is still overlooked, without intervention, competing evolution kinetically more favored over NO3RR, leaving current system far from satisfactory. Herein, based on reverse utilization Sabatier principle, series FexNiy substitutional solid-solution alloys (SSAs) are synthesized to manipulate behavior enhanced NO3RR. Upon precise optimization alloy composition, d-band center HER-active Ni shifts toward Fermi level, endowing catalyst with strong interaction greatly prolonging its lifetime, enables abundant supply facilitate As expected, maximum NH3 yield rate 31.46 mmol h-1 mg-1 delivered optimized Fe3Ni1-SSA, considerably higher than most extensively reported works. Several situ characterizations combined gain in-depth insight. Especially, Fourier transform infrared spectroscopy internal reflection mode directly observes enrichment surface, while accompanied facilitation NO3RR process verified by external mode.

Language: Английский

Citations

0
Regulation of Active Hydrogen and Nitrate Concentration: Pulsed Potential Strategies in Nitrate Electroreduction Microenvironments DOI Creative Commons
Jianping Yang, Lin Gu, Nan Song

et al.

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

Abstract The electrochemical reduction of nitrate (NO3RR) plays a significant role in the nitrogen cycle and environmental remediation. dynamics active hydrogen NO3RR were studied depth by varying concentration applying pulsed-potential approach. effect both factors on regulation degree hydrogenation intermediates product distribution was evaluated. Density functional theory (DFT) calculations indicated that elevated levels decrease energy barrier for *NO to *N conversion, enhancing *N2 formation. experimental results indicate under high concentrations, copper-palladium (CuPd) catalysts exhibit faster reaction kinetics higher selectivity. In-situ characterizations illuminated critical intermediates. CuPd catalyst achieved 95% NO3-N conversion 99% N2 selectivity at 1 M pulse potential modulation surface. Finite element analysis (FEA) verified pulsed potentials modulate local ion concentrations. present work brings closer practical applications, aiding protection balance cycle.

Language: Английский

Citations

0