The great interest in fuel cells inspires a substantial amount of research on nonprecious metal catalysts as alternatives to Pt-based oxygen reduction reaction (ORR) electrocatalysts. In this work, bimodal template-based synthesis strategies are proposed for the scalable preparation of hierarchically porous M-N-C (M = Fe or Co) single-atom electrocatalysts featured with active and robust MN 2 active moieties. Multiscale tuning of M-N-C catalysts regarding increasing the number of active sites and boosting the intrinsic activity of each active site is realized simultaneously at a singleatom scale. In addition to the antipoisoning power and high affinity for O 2 , the optimized Fe-N-C catalysts with FeN 2 active site presents a superior electrocatalytic activity for ORR with a half-wave potential of 0.927 V (vs reversible hydrogen electrode (RHE)) in an alkaline medium, which is 49 and 55 mV higher than those of the Co-N-C counterpart and commercial Pt/C, respectively. Density functional theory calculations reveal that the FeN 2 site is more active than the CoN 2 site for ORR due to the lower energy barriers of the intermediates and products involved. The present work may help rational design of more robust ORR electrocatalysts at the atomic level, realizing the significant advances in electrochemical conversion and storage devices. Single-Atom ElectrocatalystsThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.

Iron–nitrogen–carbon materials (Fe–N–C) are known for their excellent oxygen reduction reaction (ORR) performance. Unfortunately, they generally show a laggard oxygen evolution reaction (OER) activity, which results in a lethargic charging performance in rechargeable Zn–air batteries. Here porous S‐doped Fe–N–C nanosheets are innovatively synthesized utilizing a scalable FeCl3‐encapsulated‐porphyra precursor pyrolysis strategy. The obtained electrocatalyst exhibits ultrahigh ORR activity (E1/2 = 0.84 V vs reversible hydrogen electrode) and impressive OER performance (Ej = 10 = 1.64 V). The potential gap (ΔE = Ej = 10 − E1/2) is 0.80 V, outperforming that of most highly active bifunctional electrocatalysts reported to date. Furthermore, the key role of S involved in the atomically dispersed Fe–Nx species on the enhanced ORR and OER activities is expounded for the first time by ultrasound‐assisted extraction of the exclusive S source (taurine) from porphyra. Moreover, the assembled rechargeable Zn–air battery comprising this bifunctional electrocatalyst exhibits higher power density (225.1 mW cm−2) and lower charging–discharging overpotential (1.00 V, 100 mA cm−2 compared to Pt/C + RuO2 catalyst). The design strategy can expand the utilization of earth‐abundant biomaterial‐derived catalysts, and the mechanism investigations of S doping on the structure–activity relationship can inspire the progress of other functional electrocatalysts.

Despite the breakthroughs of transition-metal catalysts in enzyme mimicking, fundamental investigation on the design of efficient nanozymes at the atomic scale is still required for boosting their intrinsic activities to fill in gaps from enzymes to nanozymes. Herein, we developed a universal salt-template strategy for the fabrication of atomically dispersed Fe atoms on ultrathin nitrogen-doped carbon nanosheets characterized by a dramatically high concentration of 13.5 wt %. The proposed Fe-N-C nanozymes with densely isolated FeN 4 sites show high peroxidase-like activities and exhibit a specific activity of 25.33 U/mg, superior to Zn(Co)-N-C nanozymes. Both experiments and theoretical analysis revealed that FeN 4 sites not only lead to the strong adsorption of H 2 O 2 molecules but also weaken the bonding interaction between single Fe atom and two absorbed hydroxyl groups, lowering the energy barrier of the formation of hydroxyl radicals and therefore boosting their peroxidase-like activities. As expected, utilizing the peroxidase-like activity of Fe-N-C nanozymes, good sensitivity and selectivity for the intracellular H 2 O 2 monitoring were realized. It offers a versatile approach for the construction of densely isolated M-N-C single-atom catalysts and achieves better understanding of single sites for the peroxidase-like catalytic mechanisms.

By virtue of diverse structures and tunable properties, metal‐organic frameworks (MOFs) have presented extensive applications including gas capture, energy storage, and catalysis. Recently, synthesis of MOFs and their derived nanomaterials provide an opportunity to obtain competent oxygen reduction reaction (ORR) electrocatalysts due to their large surface area, controllable composition and pore structure. This review starts with the introduction of MOFs and current challenges of ORR, followed by the discussion of MOF‐based non‐precious metal nanocatalysts (metal‐free and metal/metal oxide‐based carbonaceous materials) and their application in ORR electrocatalysis. Current issues in MOF‐derived ORR catalysts and some corresponding strategies in terms of composition and morphology to enhance their electrocatalytic performance are highlighted. In the last section, a perspective for future development of MOFs and their derivatives as catalysts for ORR is discussed.

Single‐atom catalysts (SACs) have attracted extensive attention in the catalysis field because of their remarkable catalytic activity, gratifying stability, excellent selectivity, and 100% atom utilization. With atomically dispersed metal active sites, Fe‐N‐C SACs can mimic oxidase by activating O2 into reactive oxygen species, O2−• radicals. Taking advantages of this property, single‐atom nanozymes (SAzymes) can become a great impetus to develop novel biosensors. Herein, the performance of Fe‐N‐C SACs as oxidase‐like nanozymes is explored. Besides, the Fe‐N‐C SAzymes are applied in biosensor areas to evaluate the activity of acetylcholinesterase based on the inhibition toward nanozyme activity by thiols. Moreover, this SAzymes‐based biosensor is further used for monitoring the amounts of organophosphorus compounds.

Single-atom nanozymes (SAzymes), as novel nanozymes with atomically dispersed active sites, are of great importance in the development of nanozymes for their high catalytic activities, the maximum utilization efficiency of metal atoms, and the simple model of active sites. Herein, the peroxidase-like SAzymes with high-concentration Cu sites on carbon nanosheets (Cu–N–C) were synthesized through a salt-template strategy. With the densely distributed active Cu atoms (∼5.1 wt %), the Cu–N–C SAzymes exhibit remarkable activity to mimic natural peroxidase. Integrating Cu–N–C SAzymes with natural acetylcholinesterase and choline oxidase, three-enzyme-based cascade reaction system was constructed for the colorimetric detection of acetylcholine and organophosphorus pesticides. This work not only provides a strategy to synthesize SAzymes with abundant active sites but also gives some new insights for robust nanozyme biosensing systems.

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The development of nanotechnology provides promising opportunities for various important applications. The recent discovery of atomically-thick two-dimensional (2D) nanomaterials can offer manifold perspectives to construct versatile devices with high-performance to satisfy multiple requirements. Many studies directed at graphene have stimulated renewed interest on graphene-like 2D layered nanomaterials (GLNs). GLNs including boron nitride nanosheets, graphitic-carbon nitride nanosheets and transition metal dichalcogenides (e.g. MoS2 and WS2) have attracted significant interest in numerous research fields from physics and chemistry to biology and engineering, which has led to numerous interdisciplinary advances in nano science. Benefiting from the unique physical and chemical properties (e.g. strong mechanical strength, high surface area, unparalleled thermal conductivity, remarkable biocompatibility and ease of functionalization), these 2D layered nanomaterials have shown great potential in biochemistry and biomedicine. This review summarizes recent advances of GLNs in applications of biosensors and nanomedicine, including electrochemical biosensors, optical biosensors, bioimaging, drug delivery and cancer therapy. Current challenges and future perspectives in these rapidly developing areas are also outlined. It is expected that they will have great practical foundation in biomedical applications with future efforts.