Current Advances on the Single‐Atom Nanozyme and Its Bioapplications

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(10)

Published: Feb. 11, 2023

Nanozymes, a class of nanomaterials mimicking the function enzymes, have aroused much attention as candidate in diverse fields with arbitrarily tunable features owing to diversity crystalline nanostructures, composition, and surface configurations. However, uncertainty their active sites lower intrinsic deficiencies nanomaterial-initiated catalysis compared natural enzymes promote pursuing alternatives by imitating biological centers. Single-atom nanozymes (SAzymes) maximize atom utilization well-defined structure, providing an important bridge investigate mechanism relationship between structure catalytic activity. They risen new burgeoning alternative enzyme from vitro bioanalytical tool vivo therapy flexible atomic engineering structure. Here, focus is mainly on three parts. First, detailed overview single-atom catalyst synthesis strategies including bottom-up top-down approaches given. Then, according structural feature nanocatalysts, influence factors such central metal atom, coordination number, heteroatom doping, metal-support interaction are discussed representative applications (including antibacterial/antiviral performance, cancer therapy, biosensing) highlighted. In end, future perspective challenge facing demonstrated.

Language: Английский

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Review of Carbon Support Coordination Environments for Single Metal Atom Electrocatalysts (SACS)

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(1)

Published: April 20, 2023

This topical review focuses on the distinct role of carbon support coordination environment single-atom catalysts (SACs) for electrocatalysis. The article begins with an overview atomic configurations in SACs, including a discussion advanced characterization techniques and simulation used understanding active sites. A summary key electrocatalysis applications is then provided. These processes are oxygen reduction reaction (ORR), evolution (OER), hydrogen (HER), nitrogen (NRR), dioxide (CO

Language: Английский

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A sodium-ion-conducted asymmetric electrolyzer to lower the operation voltage for direct seawater electrolysis

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 4, 2023

Hydrogen produced from neutral seawater electrolysis faces many challenges including high energy consumption, the corrosion/side reactions caused by Cl-, and blockage of active sites Ca2+/Mg2+ precipitates. Herein, we design a pH-asymmetric electrolyzer with Na+ exchange membrane for direct electrolysis, which can simultaneously prevent Cl- corrosion precipitation harvest chemical potentials between different electrolytes to reduce required voltage. In-situ Raman spectroscopy density functional theory calculations reveal that water dissociation be promoted catalyst based on atomically dispersed Pt anchored Ni-Fe-P nanowires reduced barrier (by 0.26 eV), thus accelerating hydrogen evolution kinetics in seawater. Consequently, asymmetric exhibits current densities 10 mA cm-2 100 at voltages 1.31 V 1.46 V, respectively. It also reach 400 low voltage 1.66 80 °C, corresponding electricity cost US$1.36 per kg H2 ($0.031/kW h bill), lower than United States Department Energy 2025 target (US$1.4 H2).

Language: Английский

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Terbium-induced cobalt valence-band narrowing boosts electrocatalytic oxygen reduction

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(11), P. 5500 - 5512

Published: Jan. 1, 2023

Tb 2 O 3 endows Co 3d with a narrow band and appropriate location via 3d–O 2p–Tb 4f gradient orbital coupling to efficiently enhance the oxygen reduction reaction.

Language: Английский

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Elucidating Electrocatalytic Oxygen Reduction Kinetics via Intermediates by Time‐Dependent Electrochemiluminescence

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 2, 2023

Facile evaluation of oxygen reduction reaction (ORR) kinetics for electrocatalysts is critical sustainable fuel-cell development and industrial H2 O2 production. Despite great success in ORR studies using mainstream strategies, such as the membrane electrode assembly, rotation electrodes, advanced surface-sensitive spectroscopy, time spatial distribution reactive species (ROS) intermediates diffusion layer remain unknown. Using time-dependent electrochemiluminescence (Td-ECL), we report an intermediate-oriented method analysis. Owing to multiple ultrasensitive stoichiometric reactions between ROS ECL emitter, except electron transfer numbers rate constants, potential-dependent were successfully obtained first time. Such exclusively uncovered information would guide fuel cells production with maximized activity durability.

Language: Английский

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Recent advances and challenges in developing electrochemiluminescence biosensors for health analysis

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(24), P. 3507 - 3522

Published: Jan. 1, 2023

Recent advances and challenges in developing electrochemiluminescence biosensors for health analysis are reviewed.

Language: Английский

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NiCo‐LDH Hollow Nanocage Oxygen Evolution Reaction Promotes Luminol Electrochemiluminescence

Small, Journal Year: 2023, Volume and Issue: 20(11)

Published: Nov. 5, 2023

Abstract Conventional luminol co‐reactant electrochemiluminescence (ECL) systems suffer from low stability and accuracy due to factors such as the ease of decomposition hydrogen peroxide inefficient generation reactive oxygen species (ROS) dissolved oxygen. Inspired by ECL mechanism mediated evolution reaction (OER), nickel‐cobalt layered double hydroxide (NiCo‐LDH) hollow nanocages with structure defect state are used co‐reaction promoters enhance emission luminol‐H 2 O system. Thanks state, NiCo‐LDH show excellent OER catalytic activity, which can stabilize efficiently produce ROS emission. Additionally, mechanistic exploration suggests that involved in system derived process, there is a positive correlation between intensity activity promoter. The selection catalysts key factor improving Finally, dual‐mode immunosensor constructed for detection analysis alpha‐fetoprotein (AFP) based on promoting effect

Language: Английский

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Regulating Reactive Oxygen Species over M–N–C Single-Atom Catalysts for Potential-Resolved Electrochemiluminescence

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 12197 - 12205

Published: April 17, 2024

The development of potential-resolved electrochemiluminescence (ECL) systems with dual emitting signals holds great promise for accurate and reliable determination in complex samples. However, the practical application such is hindered by inevitable mutual interaction mismatch between different luminophores or coreactants. In this work, first time, precisely tuning oxygen reduction performance M–N–C single-atom catalysts (SACs), we present a luminol ECL system employing endogenous dissolved O2 as coreactant. Using advanced situ monitoring theoretical calculations, elucidate intricate mechanism involving selective efficient activation through central metal species modulation. This modulation leads to controlled generation hydroxyl radical (·OH) superoxide (O2·–), which subsequently trigger cathodic anodic emission, respectively. well-designed Cu–N–C SACs, their moderate oxophilicity, enable simultaneous ·OH O2·–, thereby facilitating ECL. As proof concept, employed principal component analysis statistical method differentiate antibiotics based on output dual-potential signals. work establishes new avenue constructing platform single luminophore coreactant precise regulation active intermediates.

Language: Английский

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Precise coordination of high-loading Fe single atoms with sulfur boosts selective generation of nonradicals

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(4)

Published: Jan. 17, 2024

Nonradicals are effective in selectively degrading electron-rich organic contaminants, which unfortunately suffer from unsatisfactory yield and uncontrollable composition due to the competitive generation of radicals. Herein, we precisely construct a local microenvironment carbon nitride–supported high-loading (~9 wt.%) Fe single-atom catalyst (Fe SAC) with sulfur via facile supermolecular self-assembly strategy. Short-distance S coordination boosts peroxymonosulfate (PMS) activation generates high-valent iron–oxo species IV =O) along singlet oxygen ( 1 O 2 ), significantly increasing yield, PMS utilization, p -chlorophenol reactivity by 6.0, 3.0, 8.4 times, respectively. The nonradicals is controllable simply changing content. In contrast, long-distance both radicals nonradicals, could not promote reactivity. Experimental theoretical analyses suggest that short-distance upshifts d -band center atom, i.e., being close Fermi level, changes binding mode between atom site generate =O high yield. S-coordinated SAC exhibits excellent application potential various water matrices. These findings can guide rational design robust SACs toward selective utilization.

Language: Английский

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Electroless Deposition of Palladium Nanoparticles on Graphdiyne Boosts Electrochemiluminescence

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3836 - 3843

Published: Feb. 2, 2024

Modulating the electronic structure of metal nanoparticles via metal–support interaction has attracted intense interest in field catalytic science. However, roles supporting substrates regulating properties electrochemiluminescence (ECL) remain elusive. Here, we find that use graphdiyne (GDY) as substrate for electroless deposition Pd (Pd/GDY) produces most pronounced anodic signal enhancement luminol–dissolved oxygen (O2) ECL system co-reactant accelerator over other carbon-based composite nanomaterials. Pd/GDY exhibits electrocatalytic activity reduction O2 through a four-electron pathway at approximately −0.059 V (vs Ag/AgCl) neutral solution forming reactive species (ROS) intermediates. The study shows and GDY increases amount stability ROS on electrode surface promotes reaction luminol anion radical to generate excited luminol, which significantly boosts emission. Based quenching consumption by antioxidants, develop platform detection intracellular antioxidants. This provides an avenue development efficient systems media expands biological application systems.

Language: Английский

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