Co‐Catalytic Metal‐Support Interactions Design on Single‐Atom Alloy for Boosted Electro‐Reduction of Nitrate to Nitrogen

Advanced Functional Materials, Год журнала: 2024, Номер 34(45)

Опубликована: Май 28, 2024

Abstract The past decades have seen considerable imbalances in the nitrogen cycle due to excessive use of nitrate agriculture and industry. Electrocatalytic reduction (NO 3 RR) (N 2 ) holds significant potential for addressing pollution wastewater but suffers from nitrite formation sluggish hydrogeneration process. Here a single atom alloy (SAA) catalyst featuring atomically dispersed Ru on 2D Ni metal (Ru 1 Ni), proving remarkable performance − –N conversion (≈93%) N selectivity (≈99%)) through co‐catalytic metal‐support interactions (CMSI) effect is reported. Significantly, SAA achieves NO RR removal capacity as high 11.1 mg L −1 h cm −2 with 20 cycles stability (9 per cycle), surpassing most previously reported works. core boosting lies synergistically promoted activation accelerated hydrogenation oxide intermediates site substrate, respectively, revealed by various situ experiments theoretical simulations. DFT calculations indicate electron transfer substrate more robust interaction between Ru–Ni comparison that Ni–Ni. This work offers resilient methodology rational design highly efficient electrocatalysts CMSI modulation RR, illuminating arena treatment cycle.

Язык: Английский

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Advanced Materials for NH3 Capture: Interaction Sites and Transport Pathways

Nano-Micro Letters, Год журнала: 2024, Номер 16(1)

Опубликована: Июнь 27, 2024

Abstract Ammonia (NH 3 ) is a carbon-free, hydrogen-rich chemical related to global food safety, clean energy, and environmental protection. As an essential technology for meeting the requirements raised by such issues, NH capture has been intensively explored researchers in both fundamental applied fields. The four typical methods used are (1) solvent absorption ionic liquids their derivatives, (2) adsorption porous solids, (3) ab-adsorption liquids, (4) membrane separation. Rooted development of advanced materials capture, we conducted coherent review design different materials, mainly past 5 years, interactions with molecules construction transport pathways, as well structure–property relationship, specific examples discussed. Finally, challenges current research future worthwhile directions proposed.

Язык: Английский

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An Electron Transfer Mediated Mechanism for Efficient Photoreforming of Waste Plastics Using a Ni₃S₄/ZnCdS Heterojunction

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 24, 2025

Abstract The oxidative degradation of plastics in conjunction with the production clean hydrogen (H 2 ) represents a significant challenge. Herein, Ni 3 S 4 /ZnCdS heterojunction is rationally synthesized and employed for efficient H high‐selectivity value‐added chemicals from waste plastic. By integrating spectroscopic analysis techniques density functional theory (DFT) calculations, solely electron transfer‐mediated reaction mechanism confirmed, wherein extracts electrons ZnCdS (ZCS) to promote spatial segregation photogenerated holes, which not only facilitates but also maintains high oxidation potential holes on ZCS surface, favoring hole‐dominated plastic oxidation. Notably, catalyst exhibited rates as 27.9 17.4 mmol g −1 h , along selectivity 94.2% 78.3% liquid product toward pyruvate acetate polylactic acid (PLA) polyethylene terephthalate (PET), respectively. Additionally, carbon yields 26.5% 2.2% are measured after 9 photoreforming, representing highest values reported date. Overall, this research presents promising approach converting into fuel valuable chemical products, offering solution growing issue “ White Pollution ”.

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 8012 - 8023

Опубликована: Фев. 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.

Язык: Английский

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Balancing Hydrogen Evolution and Hydrogenation Reaction via Facet Engineering for Efficient Conversion of Nitrate to Ammonia in Actual Wastewater

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Abstract Due to the competitive relationship between nitrate reduction reaction (NO 3 − RR) and hydrogen evolution (HER), conventional approach improve Faradaic efficiency is select a catalyst without HER activity. Nevertheless, such strategy not only limits application of catalysts in NO RR, but also causes insufficient source, thereby sacrificing ammonia yield rate. We believe that should be excluded from hydrogenation reduction. Herein, taking traditional water electrolysis material Co O 4 as model system, we reveal oxygen vacancies on crystal facet can greatly promote dissociation capture intermediate for successfully shifting pathway hydrogenation. Beyond development, construct hybrid reactor achieve an recovery rate 1216.8 g‐N m −2 d −1 nuclear industry wastewater with ultra‐high concentration. This study breaks through limitation which provides significant insight into designing mechanism.

Язык: Английский

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Subnanometric Nickel Phosphide Heteroclusters with Highly Active Ni^δ+–P^δ− Pairs for Nitrate Reduction toward Ammonia

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

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Oxide Support Inert in Its Interaction with Metal but Active in Its Interaction with Oxide and Vice Versa

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 9, 2025

Supported metal or oxide nanostructures catalyze many industrial reactions, where the interaction of overlayer with its support can have a substantial influence on catalytic performance. In this work, we show that small Pt species be well stabilized CeO2 under both H2-containing and O2-containing atmospheres but sintering happens SiO2, indicating is active whereas SiO2 inert in Pt-support interaction. On other hand, Co (CoOx) supported maintain low-valence Co2+ state air during CO2 hydrogenation to CO, strong CoOx SiO2. However, has weak easily reduced metallic reaction producing CH4. Thus, active, for CoOx-support interaction, which counter common sense from Pt/oxide systems. Systematic studies stability behaviors nanocatalysts various oxides reducibility supports used describe catalyst-support Oxide high low metal-oxygen bond strength interact strongly metals, showing metalphilicity. Conversely, oxides, having oxidephilicity.

Язык: Английский

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Boosting nitrate electroreduction to ammonia on atomic Ru-Co pair sites in hollow spinels

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 358, С. 124387 - 124387

Опубликована: Июль 9, 2024

Язык: Английский

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Ru Single Atoms Tailoring the Acidity of Metallic Tungsten Dioxide for a Boosted Alkaline Hydrogen Evolution Reaction

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8238 - 8251

Опубликована: Май 13, 2024

Currently, the construction of an acid-like catalyst surface in a high-pH electrolyte is advocated as one most pioneering strategies for significantly improving catalytic activity alkaline hydrogen evolution reaction. However, proton transfer kinetics that determines proton-coupled electron reaction largely dependent on usage extensive noble-metal bulk phase. Herein, well-designed dynamic system constructed by metallic WO2 matrix and supported Ru single atoms (0.89 wt %) grown nickel foam (Ru SAC@WO2/NF). The as-prepared SAC@WO2/NF free-standing exhibits superior activities with delivering current densities 10, 50, 200 mA/cm2 only requiring overpotentials ∼0, 40, 84 mV, respectively, ultralow Tafel slope (38 mV/dec) 1.0 M KOH electrolyte. Moreover, our deliberately prepared composite also shows long-term stability negligible decay after continuous generation at more than 50 h. Comprehensive spectroscopy characterizations combined density function theory calculations reveal improved can be understood two reasons: (i) contributes to environment through formation weak-acid tungsten bronze (HxWOy) intermediates solid–liquid interface electrolyte; (ii) unlike weak electronic interaction between nanoparticles HxWOy intermediates, are evidenced efficiently tailor acidity accelerated deprotonation kinetics, thus resulting regeneration active sites next cycle. Such interesting concept design driven basic chemical theories will benefit exploration but higher added-values water electrolysis beyond.

Язык: Английский

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

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Авг. 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.

Язык: Английский

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