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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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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Regioselective Doping into Atomically Aligned Core–Shell Structures for Electrocatalytic Reduction of Nitrate to Ammonia

Advanced Energy Materials, Год журнала: 2024, Номер 14(46)

Опубликована: Авг. 26, 2024

Abstract The electrochemical nitrate reduction reaction (NO 3 − RR) presents an environmentally friendly approach for efficient NO pollutant removal and ammonia (NH ) production, compared to the conventional Haber–Bosch approach. While core/shell engineering has demonstrated its potential in enhancing RR performance, significant synthetic challenges limited shell layer modification capabilities impede exploration of high‐performance catalysts. Herein, CuCoO/Co(OH) 2 structure via situ activation is synthesized. catalyst delivers a maximum NH Faradaic efficiency (FE) 94.7% at −0.5 V RHE with excellent durability selectivity over wide range potentials RR, surpassing electrocatalytic performance both undoped core components. outstanding Cu─CoO/Co(OH) ascribed enhanced charge transfer, stabilization key intermediates, regulation hydrogen adsorption Cu‐doped structure. Furthermore, assembled Zn−NO battery device attains peak current density exceeding 32 mA cm −2 yield up 145.4 µmol h −1 . work offers novel strategy sheds light on doping effects synthesis.

Язык: Английский

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Engineering Nickel Dopants in Atomically Thin Molybdenum Disulfide for Highly Efficient Nitrate Reduction to Ammonia

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 16, 2024

Abstract The electrocatalytic nitrate reduction reaction (NO 3 − RR) presents a promising pathway for achieving both ammonia (NH ) electrosynthesis and water pollutant removal simultaneously. Among various electrocatalysts explored, 2D materials have emerged as candidates due to their ability regulate electronic states active sites through doping. However, the impact of doping effects in on mechanism NO RR remains relatively unexplored. Here, Ni‐doped MoS 2 (Ni‐MoS nanosheets are investigated model system, demonstrating enhanced performance compared undoped counterparts. By controlling concentration, Ni‐MoS achieve remarkable faradic efficiency (FE) 92.3% NH at −0.3 V RHE with excellent stability. mechanistic studies reveal that elevation performances originates from generation more hydrogen acceleration nitrite facilitated by Ni Combining experimental observations theoretical calculations it is revealed appropriate level can enhance *NO adsorption strength, thereby facilitating subsequent steps. Together demonstration Zn−NO battery devices, work provides new insights into design regulation material catalysts efficient RR.

Язык: Английский

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High-Entropy Ultrathin Amorphous Metal–Organic Framework-Stabilized Ru(Mo) Dual-Atom Sites for Water Oxidation

ACS Energy Letters, Год журнала: 2024, Номер unknown, С. 5763 - 5770

Опубликована: Ноя. 6, 2024

High-entropy metal–organic frameworks (HE-MOFs) offer immense potential in electrocatalysis due to their diverse metallic compositions and high densities of active sites. Integrating bimetallic single-atom catalysts (SACs) with HE-MOFs for enhanced oxygen evolution reaction (OER) performance remains challenging. Here, we stabilize atomically dispersed Ru Mo amorphous HE-MOF nanosheets (HE(Ru,Mo)-MOFs) via situ-formed high-entropy oxides, elucidating the deprotonation mechanism. Evidence supports presence high-density O-bridged dual-atom The multimetallic composition induces electronic redistribution balances oxidation state metal sites, enhancing intrinsic OER activity. HE(Ru,Mo)-MOFs exhibit low overpotentials 267 mV@10 mA cm–2 266 alkaline freshwater industrial wastewater, respectively, exceptional durability surpassing that commercial RuO2 catalysts. Mechanistic insights reveal atomic dispersion facilitates rapid charge transfer intermediate transformation, promising advanced energy conversion.

Язык: Английский

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