Spatial Position Regulation of Cu Single Atom Site Realizes Efficient Nanozyme Photocatalytic Bactericidal Activity

Advanced Materials, Год журнала: 2023, Номер 35(46)

Опубликована: Июль 27, 2023

Recently, single-atom nanozymes have made significant progress in the fields of sterilization and treatment, but their catalytic performance as substitutes for natural enzymes drugs is far from satisfactory. Here, a method reported to improve enzyme activity by adjusting spatial position site on nanoplatforms. Two types Cu are synthesized interlayer (CuL /PHI) in-plane (CuP poly (heptazine imide) (PHI) through different synthesis pathways. Experimental theoretical analysis indicates that PHI can effectively adjust coordination number, bond length, electronic structure single atoms compared position, thereby promoting photoinduced electron migration O2 activation, enabling effective generate reactive oxygen species (ROS). Under visible light irradiation, photocatalytic bactericidal CuL /PHI against aureus ≈100%, achieving same antibacterial effect antibiotics, after 10 min low-dose exposure 2 h incubation.

Язык: Английский

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Boosting CO₂ Electroreduction over a Covalent Organic Framework in the Presence of Oxygen

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 7, 2024

Herein, we propose an oxygen-containing species coordination strategy to boost CO

Язык: Английский

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Advances on Axial Coordination Design of Single-Atom Catalysts for Energy Electrocatalysis: A Review

Nano-Micro Letters, Год журнала: 2023, Номер 15(1)

Опубликована: Окт. 13, 2023

Abstract Single-atom catalysts (SACs) have garnered increasingly growing attention in renewable energy scenarios, especially electrocatalysis due to their unique high efficiency of atom utilization and flexible electronic structure adjustability. The intensive efforts towards the rational design synthesis SACs with versatile local configurations significantly accelerated development efficient sustainable electrocatalysts for a wide range electrochemical applications. As an emergent coordination avenue, intentionally breaking planar symmetry by adding ligands axial direction metal single atoms offers novel approach tuning both geometric structures, thereby enhancing electrocatalytic performance at active sites. In this review, we briefly outline burgeoning research topic axially coordinated provide comprehensive summary recent advances synthetic strategies Besides, challenges outlooks field also been emphasized. present review provides in-depth understanding SACs, which could bring new perspectives solutions fine regulation structures catering high-performing electrocatalysis.

Язык: Английский

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Efficient and stable acidic CO ₂ electrolysis to formic acid by a reservoir structure design

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(51)

Опубликована: Дек. 12, 2023

Electrochemical synthesis of valuable chemicals and feedstocks through carbon dioxide (CO 2 ) reduction in acidic electrolytes can surmount the considerable CO loss alkaline neutral conditions. However, achieving high productivity, while operating steadily electrolytes, remains a big challenge owing to severe competing hydrogen evolution reaction. Here, we show that vertically grown bismuth nanosheets on gas-diffusion layer create numerous cavities as electrolyte reservoirs, which confine situ–generated hydroxide potassium ions limit inward proton diffusion, producing locally environments. Based this design, achieve formic acid Faradaic efficiency 96.3% partial current density 471 mA cm −2 at pH 2. When operated slim continuous-flow electrolyzer, system exhibits full-cell energy 40% single pass 79% performs over 50 h. We further demonstrate production pure aqueous solution with concentration 4.2 weight %.

Язык: Английский

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Unveiling pH‐Dependent Adsorption Strength of *CO₂⁻ Intermediate over High‐Density Sn Single Atom Catalyst for Acidic CO₂‐to‐HCOOH Electroreduction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 16, 2024

Abstract The acidic electrochemical CO 2 reduction reaction (CO RR) for direct formic acid (HCOOH) production holds promise in meeting the carbon‐neutral target, yet its performance is hindered by competing hydrogen evolution (HER). Understanding adsorption strength of key intermediates electrolyte indispensable to favor RR over HER. In this work, high‐density Sn single atom catalysts (SACs) were prepared and used as catalyst, reveal pH‐dependent coverage *CO − intermediatethat enables enhanced towards HCOOH production. At pH=3, SACs could deliver a high Faradaic efficiency (90.8 %) formation corresponding partial current density up −178.5 mA cm −2 . detailed situ attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopic studies that favorable alkaline microenvironment formed near surface SACs, even electrolyte. More importantly, intermediate unravelled which turn affects competition between HER

Язык: Английский

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Deciphering Structure‐Activity Relationship Towards CO₂ Electroreduction over SnO₂ by A Standard Research Paradigm

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(12)

Опубликована: Янв. 29, 2024

Abstract Authentic surface structures under reaction conditions determine the activity and selectivity of electrocatalysts, therefore, knowledge structure‐activity relationship can facilitate design efficient catalyst for specific reactivity requirements. However, understanding between a more realistic active its performance is challenging due to complicated interface microenvironment in electrocatalysis. Herein, we proposed standard research paradigm effectively decipher electrocatalysis, which exemplified CO 2 electroreduction over SnO . The practice has aided discovering authentic/resting states (Sn layer) accountable electrochemical reduction (CO RR) electrocatalytic conditions, then corroborated subsequent RR experiments with different morphologies (nanorods, nanoparticles, nanosheets) combination situ characterizations. This methodology further extended providing helpful insights into catalytic structures. It believed that our also applicable other systems, meantime, decreases discrepancy theory experiments, accelerates achieve sustainable energy conversion.

Язык: Английский

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p-d Orbital Hybridization Induced by Asymmetrical FeSn Dual Atom Sites Promotes the Oxygen Reduction Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21357 - 21366

Опубликована: Июль 25, 2024

With more flexible active sites and intermetal interaction, dual-atom catalysts (DACs) have emerged as a new frontier in various electrocatalytic reactions. Constructing typical p-d orbital hybridization between p-block d-block metal atoms may bring avenues for manipulating the electronic properties thus boosting activities. Herein, we report distinctive heteronuclear dual-metal atom catalyst with asymmetrical FeSn dual embedded on two-dimensional C2N nanosheet (FeSn–C2N), which displays excellent oxygen reduction reaction (ORR) performance half-wave potential of 0.914 V an alkaline electrolyte. Theoretical calculations further unveil powerful stannum ferrum sites, triggers electron delocalization lowers energy barrier *OH protonation, consequently enhancing ORR activity. In addition, FeSn–C2N-based Zn–air battery provides high maximum power density (265.5 mW cm–2) specific capacity (754.6 mA h g–1). Consequently, this work validates immense along perception into logical design DACs.

Язык: Английский

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Regulating the Electronic Configuration of Ni Sites by Breaking Symmetry of Ni‐Porphyrin to Facilitate CO₂ Photocatalytic Reduction

Advanced Functional Materials, Год журнала: 2024, Номер 34(25)

Опубликована: Фев. 10, 2024

Abstract Adapting the coordination environment to influence electronic configuration of active sites represents an efficient approach for improving photocatalytic performance CO 2 reduction reaction (CO RR) but how execute it precisely remains challenging. Herein, heteroatom‐substitution in Ni‐porphyrin break symmetry Ni center is proposed be effective solution. Based on this, two symmetry‐breaking Ni‐porphyrins, namely Ni(Cl)ON 3 Por and Ni(Cl)SN , are designed successfully prepared. By theoretical calculation, found that efficiently regulates d orbital energy levels center. Furthermore, experimental findings jointly revealed Ni‐porphyrins facilitates generation highly reactive I species during catalytic process, effectively stabilizing reducing barrier formation key * COOH intermediate. As a result, gave production rates 24.7 38.8 mmol g −1 h as well selectivity toward 94.0% 96.4%, respectively, outperforming symmetric NiN 4 rate 6.6 82.8%). These offer microscopic insights into modulate activity by tuning rational design competent catalyst RR photocatalysis.

Язык: Английский

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Addressing the Carbonate Issue: Electrocatalysts for Acidic CO₂ Reduction Reaction

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Май 9, 2024

Abstract Electrochemical CO 2 reduction reaction (CO RR) powered by renewable energy provides a promising route to conversion and utilization. However, the widely used neutral/alkaline electrolyte consumes large amount of produce (bi)carbonate byproducts, leading significant challenges at device level, thereby impeding further deployment this reaction. Conducting RR in acidic electrolytes offers solution address “carbonate issue”; however, it presents inherent difficulties due competitive hydrogen evolution reaction, necessitating concerted efforts toward advanced catalyst electrode designs achieve high selectivity activity. This review encompasses recent developments RR, from mechanism elucidation design engineering. begins discussing mechanistic understanding pathway, laying foundation for RR. Subsequently, an in‐depth analysis advancements catalysts is provided, highlighting heterogeneous catalysts, surface immobilized molecular enhancement. Furthermore, progress made device‐level applications summarized, aiming develop high‐performance systems. Finally, existing future directions are outlined, emphasizing need improved selectivity, activity, stability, scalability.

Язык: Английский

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Ultra‐Fast Pulsed Discharge Preparation of Coordinatively Unsaturated Asymmetric Copper Single‐Atom Catalysts for CO₂ Reduction

Advanced Functional Materials, Год журнала: 2024, Номер 34(16)

Опубликована: Янв. 3, 2024

Abstract Single‐atom catalysts possess great potential for applications in electrochemical carbon dioxide reduction reactions. Recently, the fast and low‐cost preparation of highly efficient single‐atom remains a challenge. Herein, high‐density current generated by pulsed discharge is employed formation graphene aerogel anchored Cu single atom perfectly. The atoms decomposed Cu(NO 3 ) 2 •xH O are fixed on under local transient high temperature intense electromagnetic field. activity selectivity formic acid correlated with coordinatively unsaturated Cu─N 1 moieties, reaching an optimal Faradaic efficiency (93.7%) at −0.9 V versus reversible hydrogen electrode (RHE). In situ characterizations reveal that asymmetric Cu─N/O structure pinched state displays better catalytic CO RR. Density functional theory results indicate sites regulate adsorption configuration intermediates lower energy barrier hydrogenation * OCHO species, thereby promoting ‐to‐HCOOH conversion.

Язык: Английский

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