Colorimetric sensor array for identifying antioxidants based on pyrolysis-free synthesis of Fe-N/C single-atom nanozymes.

Iron-anchored nitrogen/doped carbon single-atom nanozymes (Fe-N/C), which possess homogeneous active sites and adjustable catalytic environment, represent an exemplary model for investigating the structure-function relationship and catalytic activity. However, the development of pyrolysis-free synthesis technique for Fe-N/C with adjustable enzyme-mimicking activity still presents a significant challenge. Herein, Fe-N/C anchored three carrier morphologies were created via a pyrolysis-free approach by covalent organic polymers. The peroxidase-like activity of these Fe-N/C nanozymes was regulated via the pores of the anchored carrier, resulting in varying electron transfer efficiency due to disparities in contact efficacy between substrates and catalytic sites within diverse microenvironments. Additionally, a colorimetric sensor array for identifying antioxidants was developed: (1) the Fe-N/C catalytically oxidized two substrates TMB and ABTS, respectively; (2) the development of a colorimetric sensor array utilizing oxTMB and oxABTS as sensing channels enabled accurate discrimination of antioxidants such as ascorbic acid (AsA), glutathione (GSH), cysteine (Cys), gallic acid (GA), and caffeic acid (CA). Subsequently, the sensor array underwent rigorous testing to validate its performance, including assessment of antioxidant mixtures and individual antioxidants at varying concentrations, as well as target antioxidants and interfering substances. In general, the present study offered valuable insights into the active origin and rational design of nanozyme materials, and highlighting their potential applications in food analysis.

Rational design of Fe, N co-doped porous carbon derived from conjugated microporous polymer as an electrocatalytic platform for oxygen reduction reaction.

Porous iron-nitrogen-doped carbons (FeNC) offer a great platform for construction of cathodic oxygen reduction reaction (ORR) catalysts in fuel cells. However, challenges still remain regarding with the collapse of carbon-skeleton during pyrolysis, uneven distribution of active sites and aggregation of metal atoms. In this work, we synthesized Fe, N co-doped conjugated microporous polymer (FeN-CMP) through a facile bottom-up strategy using 1,3,5-triethynylbenzene and iron-chelated 3,8-dibromo-1,10-phenanthroline as monomers, ensuring the uniform coordination of N with Fe element in network. Then, the resulting FeN-CMP was treated by pyrolysis without structural collapse to obtain porous FeNC electrocatalyst for ORR. The most active catalyst was fabricated under 900 °C, which exhibits remarkable ORR activity in alkaline medium with half-wave potential of 0.796 V (18 mV and 105 mV positive deviation from the commercial Pt/C catalyst and post-doping catalyst), high selectivity with nearly 4e- transfer process and excellent methanol tolerance. Our study first developed porous FeNC electrocatalysts derived from Fe, N-anchoring CMPs based on pre-functionalization of monomers, which exhibits great potential as an alternative to commercial Pt/C catalyst for ORR, and provides a feasible strategy of developing multi-atoms doping catalysts for energy storage and conversion as well as heterogeneous catalysis.

Designing asymmetrical TMN4 sites via phosphorus or sulfur dual coordination as high-performance electrocatalysts for oxygen evolution reaction.

The development ofhighly efficient oxygen evolution reaction (OER) catalysts based on more cost-effective and earth-abundant elements is of great significance and still faces a huge challenge. In this work, a series of transition metal (TM)embedding a newly-defined monolayer carbon nitride phase is theoretically profiled and constructed as a catalytic platform for OER studies. Typically, a four-step screening strategy was proposed to rapidly identified high performance candidates and the coordination structure and catalytic performance relationship was thoroughly analyzed. Moreover, the eliminating criterion was established to condenses valid range based on the Gibbs free energy of OH*. Our results reveal that the as-constructed 2FeCN/P exhibits superior activity toward OER with an ultralow overpotential of 0.25 V, at the same time, the established 3FeCN/S configuration performed well as abifunctional OER/ORR electrocatalysis with extremely low overpotential ηOER/ηORR of 0.26/0.48 V. Overall, this work provides an effective framework for screening advanced OER catalysts, which can also be extended to other complex multistep catalytic reactions.

Simultaneously Engineering the First and Second Coordination Shells of Single Iron Catalysts for Enhanced Oxygen Reduction.

The atomically dispersed Fe-N4 active site presents enormous potential for various renewable energy conversions. Despite its already remarkable catalytic performance, the local atomic microenvironment of each Fe atom can be regulated to further enhance its efficiency. Herein, a novel conceptual strategy that utilizes a simple salt-template polymerization method to simultaneously adjust the first coordination shell (Fe-N3S1) and second coordination shell (C-S-C, a structure similar to thiophene) of Fe-N4 isolated atoms is proposed. Theoretical studies suggest that this approach can redistribute charge density in the MN4 moiety, lowering the d-band center of the metal site. This weakens the binding of oxygenated intermediates, enhancing oxygen reduction reaction (ORR) activity when compared to only implementing coordination shell regulation. Based on the above discovery, a single Fe atom electrocatalyst with the optimal Fe-N3S1-S active moiety incorporated in nitrogen, sulfur co-doped graphene (Fe-SAc/NSG) is designed and synthesized. The Fe-SAc/NSG catalyst exhibits excellent alkaline ORR activity, exceeding benchmark Pt/C and most Fe-SAc ORR electrocatalysts, as well as superior stability in Zn-air battery. This work aims to pave the way for creating highly active single metal atom catalysts through the localized regulation of their atomic structure.

Mechanism of directed activation of peroxymonosulfate by Fe-N/O unsymmetrical coordination-modulated polarized electric field.

Iron-nitrogen co-doped carbon materials as heterogeneous catalysts have attracted much attention in advanced oxidation processes involving peroxymonosulfate (PMS) due to their unique structure and enormous catalytic potential. However, there is limited research on the influence of different coordination structures on the central iron atoms. Through simple pyrolysis, we introduced oxygen atoms into the Fe-N coordination structure, constructing Fe-N/O@C catalysts with Fe-N2O2 coordination structure, and achieved efficient degradation of bisphenol A (BPA). Quenching experiments, electron paramagnetic resonance, and electrochemical analysis indicate that compared to the free radical activation pathway of Fe-N@C, high-valent iron-oxo species (≡Fe(Ⅳ) = O) are the main reactive oxygen species (ROS) in the Fe-N/O@C/PMS system. Meanwhile, we compared the differences in the oxidation states of Fe atoms and electron density in different coordination structures, revealing the formation of high-valent iron-oxo species and the mechanism of interfacial electron transfer. Therefore, this study provides new insights into the design and development of Fe-N co-doped catalysts for resource-efficient and environmentally friendly catalytic oxidation systems.

Enhancing activity and stability of FeNC catalysts through co incorporation for oxygen reduction reaction.

FeNC single atom catalysts (SACs) have attracted great interest due to their highly active FeN4 sites. However, the pyrolysis treatment often leads to inevitable metal migration and aggregation, which reduces the catalytic activity. Moreover, due to the Fenton reaction caused by FeNC in alkaline and acidic solutions, the presence of Fe and peroxide in electrodes may generate free radicals, resulting in serious degradation of the organic ionomer and the membrane. Herein, we report an original strategy of introducing Co single atoms into FeNC catalysts, forming atomically dispersed bimetallic active sites (FeCoNC) and improving the activity and stability of the catalyst. Benefiting from this strategy, FeCoNC catalyst exhibits excellent oxygen reduction reaction (ORR) activity in alkaline media (E1/2 = 0.88 V) and in acidic media (E1/2 = 0.77 V). As the cathode of Zn-air battery (ZAB), FeCoNC shows an excellent peak power density of 142.8 mW cm-2 and a specific capacity of 806.6 mAh/gZn. This work provides a novel avenue to optimize and enhance the ORR performance of atomic dispersed FeNC catalysts.

Research Progress on Atomically Dispersed Fe-N-C Catalysts for the Oxygen Reduction Reaction.

The efficiency and performance of proton exchange membrane fuel cells (PEMFCs) are primarily influenced by ORR electrocatalysts. In recent years, atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts have gained significant attention due to their high active center density, high atomic utilization, and high activity. These catalysts are now considered the preferred alternative to traditional noble metal electrocatalysts. The unique properties of M-N-C catalysts are anticipated to enhance the energy conversion efficiency and lower the manufacturing cost of the entire system, thereby facilitating the commercialization and widespread application of fuel cell technology. This article initially delves into the origin of performance and degradation mechanisms of Fe-N-C catalysts from both experimental and theoretical perspectives. Building on this foundation, the focus shifts to strategies aimed at enhancing the activity and durability of atomically dispersed Fe-N-C catalysts. These strategies encompass the use of bimetallic atoms, atomic clusters, heteroatoms (B, S, and P), and morphology regulation to optimize catalytic active sites. This article concludes by detailing the current challenges and future prospects of atomically dispersed Fe-N-C catalysts.

Axially Coordinated Gold Nanoclusters Tailoring Fe-N-C Nanozymes for Enhanced Oxidase-Like Specificity and Activity.

Metal-organic frameworks (MOF) derived nitrogen-doped carbon-supported monodisperse Fe (Fe-N-C) catalysts are intensively studied, but great challenges remain in understanding the relationship between the coordination structure and the performance of Fe-N-C nanozymes. Herein, a novel nanocluster ligand-bridging strategy is proposed for constructing Fe-S1 N4 structures with axially coordinated S and Au nanoclusters on ZIF-8 derived Fe-N-C (labeled Aux /Fe-S1 N4 -C). The axial Au nanoclusters facilitate electron transfer to Fe active sites, utilizing the bridging ligand S as a medium, thereby enhancing the oxygen adsorption capacity of composite nanozymes. Compared to Fe-N-C, Aux /Fe-S1 N4 -C exhibits high oxidase-like specificity and activity, and holds great potential for detecting acetylcholinesterase activity with a detection limit of 5.1 µU mL-1 , surpassing most reported nanozymes.

Effect of Phosphorus Modulation in Iron Single-Atom Catalysts for Peroxidase Mimicking.

Fe-N-C single-atom catalysts (SACs) exhibit excellent peroxidase (POD)-like catalytic activity, owing to their well-defined isolated iron active sites on the carbon substrate, which effectively mimic the structure of natural peroxidase's active center. To further meet the requirements of diverse biosensing applications, SAC POD-like activity still needs to be continuously enhanced. Herein, a phosphorus (P) heteroatom is introduced to boost the POD-like activity of Fe-N-C SACs. A 1D carbon nanowire (FeNCP/NW) catalyst with enriched Fe-N4 active sites is designed and synthesized, and P atoms are doped in the carbon matrix to affect the Fe center through long-range interaction. The experimental results show that the P-doping process can boost the POD-like activity more than the non-P-doped one, with excellent selectivity and stability. The mechanism analysis results show that the introduction of P into SAC can greatly enhance POD-like activity initially, but its effect becomes insignificant with increasing amount of P. As a proof of concept, FeNCP/NW is employed in an enzyme cascade platform for highly sensitive colorimetric detection of the neurotransmitter acetylcholine.

Mn Single-Atom Tuning Fe-N-C Catalyst Enables Highly Efficient and Durable Oxygen Electrocatalysis and Zinc-Air Batteries.

Fe-N-C catalyst is one of most promising candidates for oxygen electrocatalysis reaction in zinc-air batteries (ZABs), but achieving sustained high activity is still a challenging issue. Herein, we demonstrate that introducing Mn single atoms into Fe-N-C (Mn1@Fe-N-C/CNTs) enables the realization of highly efficient and durable oxygen electrocatalysis performance and application in ZABs. Multiple characterizations confirm that Mn1@Fe-N-C/CNTs is equipped with Mn-N2O2 and Fe-N4 sites and Fe nanoparticles. The Mn-N2O2 sites not only tune the electron structure of Fe-Nx sites to enhance intrinsic activity, but also scavenge the attack of radicals from Fe-Nx sites for improvement in ORR durability. As a result, Mn1@Fe-N-C/CNTs exhibits enhanced ORR performance to traditional Fe-N-C catalysts with high E1/2 of 0.89 V vs reversible hydrogen electrode (RHE) and maintains ORR activity after 15 000 CV. Impressively, Mn1@Fe-N-C/CNTs also presents excellent OER activity and the difference (ΔE) between E1/2 of ORR and OER potential at 10 mA cm-2 (Ej10) is only 0.59 V, outperforming most reported catalysts. In addition, the maintainable bifunctional activity of Mn1@Fe-N-C/CNTs is demonstrated in ZABs with almost unchanged cycle voltage efficiency up to 200 h. This work highlights the critical role of Mn single atoms in enhancing ORR activity and stability, promoting the development of advanced catalysts.

A first principles analysis of potential-dependent structural evolution of active sites in Fe-N-C catalysts.

Fe-N-C (iron-nitrogen-carbon) electrocatalysts have emerged as potential alternatives to precious metal-based materials for the oxygen reduction reaction (ORR). However, the structure of these materials under electrochemical conditions is not well understood, and their poor stability in acidic environments poses a formidable challenge for successful adoption in commercial fuel cells. To provide molecular-level insights into these complex phenomena, we combine periodic density functional theory (DFT) calculations, exhaustive treatment of coadsorption effects for ORR reaction intermediates, including O and OH, and comprehensive analysis of solvation stabilization effects to construct voltage-dependent ab initio thermodynamic phase diagrams that describe the in situ structure of the active sites. These structures are further linked to activity and stability descriptors that can be compared with experimental parameters such as the half-wave potential for ORR and the onset potential for carbon corrosion and CO2 evolution. The results indicate that pyridinic Fe sites at zigzag carbon edges, as well as other edge sites, exhibit high activity for ORR compared to sites in the bulk. However, edges neighboring the active sites are prone to instability via overoxidation and consequent site loss. The results suggest that it could be beneficial to synthesize Fe-N-C catalysts with small sizes and large perimeter edge lengths to enhance ORR activity, while voltage fluctuations should be limited during fuel cell operation to prevent carbon corrosion of overoxidized edges.

Engineering Fe-N4 Electronic Structure with Adjacent Co-N2C2 and Co Nanoclusters on Carbon Nanotubes for Efficient Oxygen Electrocatalysis.

Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement. Unlike the previously reported single-atom or dual-atom configurations, we designed a new type of binary-atom catalyst, through engineering Fe-N4 electronic structure with adjacent Co-N2C2 and nitrogen-coordinated Co nanoclusters, as oxygen electrocatalysts. The resultant optimized electronic structure of the Fe-N4 active center favors the binding capability of intermediates and enhances oxygen reduction reaction (ORR) activity in both alkaline and acid conditions. In addition, anchoring M-N-C atomic sites on highly graphitized carbon supports guarantees of efficient charge- and mass-transports, and escorts the high bifunctional catalytic activity of the entire catalyst. Further, through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses, the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed. This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior. It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M-N-C catalysts.

Electronic Asymmetry Engineering of Fe-N-C Electrocatalyst via Adjacent Carbon Vacancy for Boosting Oxygen Reduction Reaction.

Single-atomic transition metal-nitrogen-carbon (M-N-C) structures are promising alternatives toward noble-metal-based catalysts for oxygen reduction reaction (ORR) catalysis involved in sustainable energy devices. The symmetrical electronic density distribution of the M─N4 moieties, however, leads to unfavorable intermediate adsorption and sluggish kinetics. Herein, a Fe-N-C catalyst with electronic asymmetry induced by one nearest carbon vacancy adjacent to Fe─N4 is conceptually produced, which induces an optimized d-band center, lowered free energy barrier, and thus superior ORR activity with a half-wave potential (E1/2 ) of 0.934 V in a challenging acidic solution and 0.901 V in an alkaline solution. When assembled as the cathode of a Zinc-air battery (ZAB), a peak power density of 218 mW cm-2 and long-term durability up to 200 h are recorded, 1.5 times higher than the noble metal-based Pt/C+RuO2 catalyst. This work provides a new strategy on developing efficient M-N-C catalysts and offers an opportunity for the real-world application of fuel cells and metal-air batteries.

Degradation of enrofloxacin by a novel Fe-N-C@ZnO material in freshwater and seawater: Performance and mechanism.

In this study, we investigated the doping of Fe-N-C with ZnO (Fe-N-C@ZnO) to enhance its performance in the reduction of biological toxicity and degradation of enrofloxacin (ENR) in seawater. The steady-state/transient fluorescence analysis and free radical quenching test indicated an extremely low electron-hole recombination rate and the generation of reactive oxygen species in Fe-N-C@ZnO, leading to an improvement in the energy efficiency. We compared the ENR degradation efficiencies of Fe-N-C@ZnO and ZnO using both freshwater and seawater. In freshwater, Fe-N-C@ZnO exhibited a slightly higher degradation efficiency (95.00%) than ZnO (90.30%). However, the performance of Fe-N-C@ZnO was significantly improved in seawater compared to that of ZnO. The ENR degradation efficiency of Fe-N-C@ZnO (58.87%) in seawater was 68.39% higher than that of ZnO (34.96%). Furthermore, the reaction rate constant for ENR degradation by Fe-N-C@ZnO in seawater (7.31 × 10-3 min-1) was more than twice that of ZnO (3.58 × 10-3 min-1). Response surface analysis showed that the optimal reaction conditions were a pH of 7.42, a photocatalyst amount of 1.26 g L-1, and an initial ENR concentration of 6.56 mg L-1. Fe-N-C@ZnO prepared at a hydrothermal temperature of 128 °C and heating temperature of 300 °C exhibited the optimal performance for the photocatalytic degradation of ENR. Based on liquid chromatography-mass spectrometry analysis, the degradation processes of ENR were proposed as three pathways: two piperazine routes and one quinolone route.

Building Atomic Scale and Dense Fe─N4 Edge Sites of Highly Efficient Fe─N─C Oxygen Reduction Catalysts Using a Sacrificial Bimetallic Pyrolysis Strategy.

Replacing high-cost and scarce platinum (Pt) with transition metal and nitrogen co-doped carbon (M/N/C, M = Fe, Co, Mn, and so on) catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells has largely been impeded by the unsatisfactory ORR activity of M/N/C due to the low site utilization and inferior intrinsic activity of the M─N4 active center. Here, these limits are overcome by using a sacrificial bimetallic pyrolysis strategy to synthesize Fe─N─C catalyst by implanting the Cd ions in the backbone of ZIF-8, leading to exposure of inaccessible FeN4 edge sites (that is, increasing active site density (SD)) and high fast mass transport at the catalyst layer of cathode. As a result, the final obtained Fe(Cd)─N─C catalyst has an active site density of 33.01 µmol g-1 (with 33.01% site utilization) over 5.8 times higher than that of Fe─N─C catalyst. Specially, the optimal catalyst delivers a high ORR performance with a half-wave potential of 0.837 (vs RHE) in a 0.1 m HClO4 electrolyte, which surpasses most of Fe-based catalysts.

d-Orbital Electron Delocalization Realized by Axial Fe4 C Atomic Clusters Delivers High-Performance Fe-N-C Catalysts for Oxygen Reduction Reaction.

Fe-N-C catalyst for oxygen reduction reaction (ORR) has been considered as the most promising nonprecious metal catalyst due to its comparable catalytic performance to Pt in proton exchange membrane fuel cells (PEMFCs). The active centers of Fe-pyrrolic N4 have been proven to be extremely active for ORR. However, forming a stable Fe-pyrrolic N4 structure is a huge challenge. Here, a Cyan-Fe-N-C catalyst with Fe-pyrrolic N4 as the intrinsic active center is constructed with the help of axial Fe4 C atomic clusters, which shows a half-wave potential of up to 0.836 V (vs. RHE) in the acid environment. More remarkably, it delivers a high power density of 870 and 478 mW cm-2 at 1.0 bar in H2 -O2 and H2 -Air fuel cells, respectively. According to theoretical calculation and in situ spectroscopy, the axial Fe4 C can provide strong electronic perturbation to Fe-N4 active centers, leading to the d-orbital electron delocalization of Fe and forming the Fe-pyrrolic N4 bond with high charge distribution, which stabilizes the Fe-pyrrolic N4 structure and optimizes the OH* adsorption during the catalytic process. This work proposes a new strategy to adjust the electronic structure of single-atom catalysts based on the strong interaction between single atoms and atomic clusters.

Hierarchical porous Fe-N/C@surfactant composites synthesized by a surfactant-assisted strategy as high-performance bifunctional oxygen electrodes for rechargeable zinc-air batteries.

Herein, a soft-template strategy involving the cationic surfactants has been successfully applied to size-controlled synthesis of hierarchical porous Fe-N/C for the first time. Specifically, a small amount of Fe and cationic surfactants can be uniformly doped into the zinc-based zeolite imidazole framework (ZIF-8) crystal particles and the cationic surfactants play a critical role in the formation of hierarchically porous Fe-ZIF-8@surfactant precursors. When the Fe-ZIF-8@surfactant is subsequently pyrolyzed, atomically dispersed Fe-Nx coordination structures can be in-situ converted to Fe-N/C, while the cationic surfactants decompose to form a carbon matrix to encapsulate the active sites, thereby preventing the aggregation of nanoparticles to a certain extent. As a result, the combined Fe nanocrystals and atomically dispersed Fe-Nx in the graphitic carbon matrix generate a synergistic effect to boost the electrocatalytic behaviors with a more positive half-wave potential (0.92 V) for oxygen reduction reaction (ORR) and a lower overpotential (420 mV at 10 mA cm-2) for oxygen evolution reaction (OER). As a proof of concept, the Fe-N/C@TTAB based zinc-air batteries (ZABs) present an outstanding peak power density (107.9 mW cm-2) and a superior specific capacity (706.3 mAh g-1) with robust cycling stability over 900 cycles for 150 h, which are better than the commercial Pt/C + IrO2 based ZABs.

A Fe Single Atom Seed-Mediated Strategy Toward Fe3 C/FeNC Catalysts with Outstanding Bifunctional ORR/OER Activities.

The discovery of low-cost and high-performance bifunctional oxygen electrocatalysts is vital to the future commercialization of rechargeable zinc-air batteries (ZABs). Herein, a Fe single atom seed-mediated strategy is reported for the fabrication of Fe3 C species closely surrounded by FeN4 C active sites with strong electronic interactions built between them and more importantly, creating optimized coordination environment, via subtly adjusting their ratio, for favorable adsorption energies of oxygen intermediates formed during oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Concretely, the voltage difference (ΔE) between the ORR half-wave and OER potential at a current density of 10 mA cm-2 for the compositionally-optimized FeNC/Fe3 C-op electrocatalyst is only 0.668 V, endowing itself one of the best bifunctional OER/ORR benchmarks. As a demo, ZABs assembled with FeNC/Fe3 C-op as the air cathode deliver a remarkable specific capacity (818.1 mAh gZn -1 ) and a power density (1013.9 mWh gZn -1 ), along with excellent long-term durability (>450 h). This work extends the methodology to modulate the activity of FeN4 C atomic site, undoubtedly inspiring wide explorations on the precise design of bifunctional oxygen electrocatalysts.

A plasma-assisted approach to enhance density of accessible FeN4 sites for proton exchange membrane fuel cells.

Enhancing the density and utilization of FeN4 sites can serve as a viable approach to enhance the catalytic efficacy of iron nitrogen carbon (FeNC) catalysts for oxygen reduction reaction (ORR). Herein, we present a plasma-assisted method for enhancing the porosity of nitrogen-doped carbon. Our findings indicate that the ideal ratio of mesopore to micropore area is 0.463. This ratio not only promotes the diffusion of Fe3+ but also creates additional active sites for Fe3+ loading, leading to an increase in the number of available FeN4 sites in FeNC electrocatalysts during pyrolysis. The density (76.5 µmol g-1) and utilization (21.08 %) of d-FeNC-30 are significantly higher than those of FeNC without plasma treatment, with a 2.8-fold and 2-fold increase, respectively. Remarkably, it displays outstanding performance, evidenced by a half-wave potential of 0.835 V (vs. RHE) in a 0.1 M HClO4 solution and a power density of 0.860 W cm-2 in proton exchange membrane fuel cells (PEMFCs). The developed plasma-assisted approach for improving the site density (SD) and utilization of FeN4 provides a new perspective for high-performance ORR FeNC catalysts.

Single-Atom Fe Nanozyme with Enhanced Oxidase-like Activity for the Colorimetric Detection of Ascorbic Acid and Glutathione.

Single-atom nanozymes (SAzymes) have drawn ever-increasing attention due to their maximum atom utilization efficiency and enhanced enzyme-like activity. Herein, a facile pyrolysis strategy is reported for the synthesis of the iron-nitrogen-carbon (Fe-N-C) SAzyme using ferrocene trapped within porous zeolitic imidazolate framework-8 (ZIF-8@Fc) as a precursor. The as-prepared Fe-N-C SAzyme exhibited exceptional oxidase-mimicking activity, catalytically oxidizing 3,3',5,5'-tetramethylbenzidine (TMB) with high affinity (Km) and fast reaction rate (Vmax). Taking advantage of this property, we designed two colorimetric sensing assays based on different interaction modes between small molecules and Fe active sites. Firstly, utilizing the reduction activity of ascorbic acid (AA) toward oxidized TMB (TMBox), a colorimetric bioassay for AA detection was established, which exhibited a good linear range of detection from 0.1 to 2 µM and a detection limit as low as 0.1 µM. Additionally, based on the inhibition of nanozyme activity by the thiols of glutathione (GSH), a colorimetric biosensor for GSH detection was constructed, showing a linear response over a concentration range of 1-10 µM, with a detection limit of 1.3 µM. This work provides a promising strategy for rationally designing oxidase-like SAzymes and broadening their application in biosensing.