Coordination Structure Research Articles

Effectiveness of the Palestinian Civil Police’s Accountability and Complaint System

Objectives: This study aims to assess the effectiveness of the Palestinian Police’s accountability and complaints system, especially in light of the existing paradox in assessing the nature and role of the police. Essentially, the main goal of the police is to protect the rights and freedom of citizens; however, their authority might be abused by resorting to verbal and physical assaults against suspects and offenders under the pretext that these are essential to the task of crime control. Methods: The study uses the descriptive analytical approach, as well as the empirical method to obtain statistics and data provided by official and non-official human rights institutions. Interviews were held with decision-makers in the civil police force, relevant human rights organizations and international and foreign organizations situated in Palestine. Face-to-face and phone interviews were held with some victims who filed complaints against police officers. Results: The findings can be summarized by a lack of a clear conceptual structure and lack of coordination between accountability units. Moreover, the complaints system suffers from a duplication of complaints units across different institutions, which causes a depletion of the already scarce financial support. Conclusions: The study concludes that the Palestinian police should simplify the structure of the accountability and complaints system, ensure public access to accountability units, and pay particular attention to complaints filed by marginalized and vulnerable individuals, especially women, children and the physically challenged.

Superior single-atom and single-cluster catalysts towards electrocatalytic nitrogen reduction reactions: a theoretical perspective

The traditional Haber-Bosch process for ammonia synthesis is both energy-intensive and capital-demanding. Electrocatalytic nitrogen reduction reaction (NRR) has emerged as a promising, sustainable alternative, with recent advantages highlighting its potential. Single-atom catalysts (SACs) and single-cluster catalysts (SCCs) are promising catalysts for NRR due to their atomically dispersed active sites, maximized atom utilization, and distinctive coordination and electronic structures, all of which facilitate mechanism insights at the atomic level. Benefiting from efficient atom utilization, for example, the ammonia yield rate on Au1/C3N4 is roughly 22.5 times as high as that of supported Au nanoparticles, fully demonstrating the significant advantages of SACs over nanoparticles. In this review, we focus on the theoretical progress in SACs and SCCs for electrocatalyzing NRR, including nitrogenase-like bio-inspired catalysts and other metal-based catalysts. We further examine key adsorption energy and electronic descriptors that enhance our understanding of catalytic performance. Finally, we discuss the remaining challenges and future directions for advancing SACs and SCCs in electrocatalytic NRR applications.

High‐throughput Design of Single‐atom Catalysts with Nonplanar and Triple Pyrrole‐N Coordination for Highly Efficient H2O2 Electrosynthesis

AbstractSingle‐atom catalysts (SACs) with nonplanar configurations possess unique capabilities for tailoring the oxygen reduction reaction (ORR) catalytic performance compared with the ones with planar configurations, owing to the additional orbital rearrangement arising from the asymmetric coordination atoms. However, the systematic investigation of these nonplanar SACs has long been hindered by the difficulty in screening feasible nonplanar configurations and precisely controlling the coordination structures. Herein, we demonstrate a combined high‐throughput screening and experimental verification of nonplanar SACs (ppy‐MN3) with metal atoms triple‐coordinated by pyrrole‐N, for highly active and selective 2e− ORR electrocatalysis. With the additional p‐orbital rearrangement of N‐ligands for ppy‐MN3 during catalysis, a new descriptor on the energy difference between d‐band center of metal sites and p‐band centers of N‐ligands (Δϵd−p) is proposed to accurately identify the relationship between their catalytic activities and electronic structures, on top of the conventional d‐band center theory. Consequently, ppy‐ZnN3 is identified with excellent 2e− ORR activity (η=0.08 eV) and selectivity, as well as a low 2e− ORR kinetic barrier under alkaline condition owing to a strong hydrogen bonding between OOH* intermediate and interfacial water, which is then experimentally verified by its high electrocatalytic H2O2 yield (43 mol g−1 h−1) and selectivity (92 %) under alkaline condition. This study thus presents a proof‐of‐concept demonstration of the performance‐oriented and precise coordination design of nonplanar SACs for efficient H2O2 electrosynthesis, and, more importantly, provides an essential complement to the d‐band theory for more accurately predicting the catalytic activities of catalysts with nonplanar configurations for series potential electrochemical processes.

Simple and Smart Metal-Phenolic Micelles for Optimizing Immunotherapy by Disrupting Tumor Stemness.

cGAS-STING pathway activation has attracted considerable attention in antitumor immunotherapy, but clinical outcomes lag behind expectations due to overlooked negative feedback mechanisms. Here, we determine that STING activation promotes tumor stemness, which weakens the efficacy of STING-based therapies, presenting a double-edged sword. To address this therapeutic paradox, a simple metal-phenolic polymeric micelle (HMQ) was developed, in which Mn2+ (a STING agonist) is coordinated with quercetin (a stemness inhibitor) and hyaluronic acid (HA), to unlock the full therapeutic potential of the cGAS-STING pathway. This unique coordination structure integrates active targeting with rapid and pH-responsive drug release. Importantly, the released drugs remained in their original form, avoiding potential changes in bioactivity. HMQ effectively mitigates the stemness-promoting effects of STING activation, thus significantly amplifying the potency of cGAS-STING-based therapies. This intelligent and facile HMQ establishes a new generation of cGAS-STING agonists with promising clinical translatability and provides a flexible platform for the win-win strategy.

Regulation of the coordination number of Zn single atoms to boost electrochemical sensing of H2O2.

Compared with transition metals with partially occupied 3d orbitals, Zn has a filled 3d10 configuration, which severely restricts electron mobility and hence usually renders Zn2+ intrinsically inactive for electrochemical sensing. Metal single-atom catalysts are a new kind of sensing material. Owing to their unique coordination structure and high atomic utilization rate, metal single-atom catalysts show unique properties, which makes them promising for use in the field of electrochemical sensing. However, whether Zn single atoms are active sites remains to be elucidated. In this study, we prepared nitrogen-doped carbon (NC) materials by pyrolyzing ZIF-8 at high temperatures and reported that when the pyrolysis temperature was 800 °C, many Zn single atoms with Zn-N4 coordination structures remained in the NC material. Even when the pyrolysis temperature is increased to 1000 °C, a small number of Zn single atoms remain, and the coordination structure changes from Zn-N4 to Zn-N3. Furthermore, unexpectedly, both residual Zn single atoms showed electrocatalytic activity for H2O2 reduction. In particular, the electrocatalytic activity was significantly enhanced after the coordination structure was changed from Zn-N4 to Zn-N3. Density functional theory (DFT) calculations indicate that the coordination structure of Zn-N3 optimizes the adsorption and desorption strength of oxygen-containing species in the electrocatalytic reaction process, which lowers the energy barrier of the rate-determining step and increases the detection sensitivity of H2O2 nearly 4.1 times. This study revealed new properties of Zn single atoms for the electrocatalytic reduction of H2O2 and developed a strategy to increase the electrocatalytic activity of metal single-atom catalysts through coordination number regulation, which lays the foundation for the use of Zn single atoms in the field of electrochemical sensing and provides ideas for the design of new highly active sensing materials.

Theoretical Study on the Generation Mechanism of Intermediates During Discharge/Charge Processes in Lithium‐Air Batteries

AbstractIn this paper, molecular dynamics (MD) was used to investigate the problem of the generation mechanism of product intermediates in the aprotic electrolyte in lithium‐air batteries. Through the utilisation of simulations of the electrolyte system, molecular orbitals of the electrolyte, thermodynamic analysis of the product intermediates' reactions, the Li+ solvation structure, the electrochemical stability of the electrolyte, the Li+ and O2‐ diffusion coefficients, and the Gibb's free energy of the Li+‐O2‐ and Li+‐C2O62− were investigated in detail. The results show that the Li+ coordination structure was a contact ion pair (CIP) structure, and the formation of a 5‐coordination structure with oxygen atoms was lower in energy and more stable in structure. The TEGDME‐LiTFSI electrolyte was the most stable in electrochemistry. The Gibbs free energy of the generated Li+‐O2− and Li+‐C2O62‐ was negative, indicating that the reaction can proceed spontaneously at ambient temperature. The intermediate products were present in the electrolyte in the form of [Li(solvent)n+‐O2‐] and [Li(solvent)n+‐C2O62‐]. The study of the mechanism of product intermediates in the lithium‐air battery is important for scholars to analyze the product growth pathway and improve the battery performance.

Local structure and thermophysical properties of the molten salt FNaBe through ab initio molecular dynamics and experimental measurements

NaF-BeF2 molten salt has been proposed as one of the potential solvents and coolants for molten salt reactor due to its pertinent properties and satisfactory neutron capture cross-section. The experimental measurements combined theoretical simulations were employed to investigate comprehensive information on the structures and thermophysical properties of molten NaF-BeF2. Specifically, the specific heat capacity, density, and viscosity of NaF-BeF2 systems were determined using custom devices. Using the fitting relationships and simulations, the extrapolative data were also successfully obtained under the critical temperatures. The local structure including bond lengths, coordination structures and the potential of mean force, was further simulated by ab initio molecular dynamics in the temperature range of 673-1123 K. The coordination of Na and Be is predominantly characterized by six-fold and four-fold, respectively. Moreover, of Be-F bond is 7 times than Na-F bond, which suggests the stronger stability of Be-F bond in molten NaF-BeF2.

A review on the active sites for titanium species in zeolites: coordination structure, synthetic strategies and activity

This review provides a comprehensive overview of contemporary advances in titanosilicate zeolites. The regulatory strategies, detection methods, and catalytic properties of titanium species are comprehensively summarized.

The effect of carbon supports on the electrocatalytic performance of Ni-N-C catalysts for CO2 reduction to CO

Carbon-supported nickel and nitrogen co-doped (Ni-N-C) catalysts have been extensively studied as selective and active catalysts for CO2 electroreduction to CO. Most studies have focused on adjusting the coordination structure of Ni-Nx active sites, while the impact of the carbon supports has often been overlooked. In this study, a series of Ni-N-C catalysts on different carbon supports, including carbon black (CB), multi-walled carbon nanotubes (CNT), and activated nitrogen-doped biochar (ANBC), were synthesized using a ligand-mediated method. The effect of the carbon support on the electrocatalytic performance for CO2 reduction was investigated at both low current densities, in a H-cell, and high current densities, in a MEA electrolyzer. All of the prepared Ni-N-C catalysts show good faradaic efficiencies (FE) toward CO production (up to ~90%), however, the onset potentials and partial current densities for CO production vary greatly. The textural properties of the carbon support and the distribution of Ni-Nx active sites on the carbon support are demonstrated as the main factors behind the performance differences. In particular, hierarchical porous structures with large specific surface area are helpful to facilitate mass transport and improve the dispersion of active sites, which allows for a better CO2 reduction performance of Ni-N-ANBC compared to Ni-N-CB and Ni-N-CNT. This study demonstrates the importance of the carbon support for Ni-N-C catalysts and provides new insights into the design of efficient Ni-N-C catalysts for the CO2RR.

Active site-inspired multicopper laccase-like nanozymes for detection of phenolic and catecholamine compounds.

Phenolic compounds are typical organic pollutants which cause severe human health problems due to their teratogenesis, carcinogenesis, neurotoxicity, immunotoxicity and endocrine disruption. Natural laccase is a multicopper oxidase existing in bacteria, plants, and insects, which can accelerate the transformation of phenolic compounds to their less hazardous oxidized products under mild conditions without harmful byproducts. Despite eco-environmentally friendly property of laccase, it still faces constraints of widespread application attribute to its high cost, complex preparation, and vulnerability. Therefore, exploring laccase mimics with high catalytic activity attracts a lot of attention and endeavors. In this research, copper-based nanozymes were prepared with coordination of copper ions and imidazole for mimicking the active sites of natural laccase via solvothermal method. The obtained Cu-based (Cu-Im) nanozymes exhibited multiple redox valence states of Cu and laccase-mimicking coordination structures, which endow Cu-Im with high laccase-like activity. During the process of catalytic oxidation reactions, singlet oxygen and superoxide anions generated from oxygen. Encouraged by the catalytic property, Cu-Im was utilized in degradation and detection of phenolic and catecholamine compounds. The catalytic degradation of compounds by Cu-Im showed good conversion and substrate versatility, which can be used as a kind of potential materials for phenolic pollutant degradation and remediation. Simultaneously, colorimetric sensors of phenols and catecholamines based on Cu-Im in solution system and POCT pad platform were constructed which indicated wide linear range and low limit of detection for both detection strategies. The Cu-Im-based sensor was a promising method for sensitive, fast, convenient, and qualitative-quantitative colorimetric analysis of phenols and catecholamines. The outcomes of this research elucidate Cu-Im is a satisfactory substitute for natural laccase, which will have broad application prospects in laccase-related fields, such as environmental recovery, pollution monitoring, and diagnosis of neurological diseases etc.

Selective leaching mechanisms of zinc from industrial waste using hybrid acids: Sustainable synthesis of Nano-ZnO

Zinc-containing dust (ZCD) has received extensive attention because it is a hazardous waste rich in various metals. This study innovatively proposed a hybrid acid leaching agent based on malic acid (MA) and sulfuric acid to selectively extract Zn from ZCD and successfully prepare nano-ZnO materials. The leaching experiments show that among the combinations of various organic acids and sulfuric acid, MA and sulfuric acid are superior in the selective leaching of Zn. Under optimal conditions, the leaching ratios of Zn, Pb, and Fe are 97.70%, 0.88%, and 2.95%, respectively. In addition, the use of hybrid acids can reduce sulfuric acid consumption by more than 46%. The Molecular dynamics simulation indicate that the interaction between the hybrid acid with ZnO and PbO was stronger (PbO > ZnO > Fe2O3). The radial distribution function (RDF) reveals that Zn and Pb ions form strong coordination structures with some oxygen atoms in MA, thereby confirming that MA plays a crucial role in preventing the dissolution of Fe. Finally, spherical nano-ZnO with a purity of 98.14% and an average particle size of 68.60 nm is obtained from the leaching solutions by precipitation method. This study provides a green and sustainable alternative for the selective recovery of Zn from ZCD.

Atomically Dispersed Dual Metal Sites Anchored Catalyst Enables Photothermally Augmented Catalytic Oxidation for Biocatalytic Tumor Therapy

AbstractSingle‐atom nanozymes (SAzymes) can maximize atomic utilization efficiency and construct highly active catalytic sites for biomedical applications. Herein, atomically dispersed iron (Fe) and cobalt (Co) dual sites anchored N‐doped graphene carbon (FeCoCN) catalyst is rationally constructed to achieve photothermally augmented catalytic oxidation for effective biocatalytic tumor nanotherapy. Compared with Fe SAzyme, FeCoCN SAzyme can significantly accelerate the charge transfer and improve the activity of catalytic reactions. Co‐doping optimizes coordination structure and charge redistribution by facilitating the ratio of Fe2+ and regulating charge transfer between different metal sites and nearby coordination atoms. Bimetallic FeCoCN SAzyme possessed an ultra‐high affinity for substrate H2O2, and the catalytic kinetic Km value (0.589 mm) is superior to natural catalase and most reported nanozymes. The boosted catalytic activity in producing •OH is identified by density functional theory (DFT) studies. In vivo, investigation demonstrates that atomically dispersed Fe and Co dual sites anchored FeCoCN SAzyme significantly suppresses tumor proliferation under NIR laser irradiation by photothermally enhanced catalytic oxidation. Additionally, Fe‐ and Co‐doping in FeCoCN make it suitable as a tracer for T2 magnetic resonance imaging. This work provides a paradigm to rationally design bimetallic SAzymes with enhanced biocatalytic performance for tumor treatment.

Modulation of the Second-Beyond Coordination Structure in Single-Atom Electrocatalysts for Confirmed Promotion of Ammonia Synthesis.

Although microenvironments surrounding single-atom catalysts (SACs) have been widely demonstrated to have a remarkable effect on their catalytic performances, it remains unclear whether the local structure beyond the secondary coordination shells works as well or not. Herein, we employed a series of metal-organic frameworks (MOFs) with well-defined and tunable second-beyond coordination spheres as model SAC electrocatalysts to discuss the influence of long-distance structure on the ammonia synthesis from nitrate, which were synthesized and denoted as Cu12-NDI-X (X = NMe2, H, F). It is first experimentally confirmed that the remote substitution of function groups beyond the secondary coordination sphere can remarkably affect the activity of ammonia synthesis. Meanwhile, the -H endowed Cu12-NND-H exhibits a superior ammonia yield (35.1 mg·h-1·mgcat-1) and FE (98.7%) to those modified with -NMe2 and -F, which also shows good stability at 100 mA·cm-2. The remarkable promotion of the modulated second-beyond coordination structure is unraveled to result from the adjustable d-band center of the Cu active site leading to promoted adsorption of the NO3- and protonation of key intermediates. Encouraged by its extraordinary ammonia yield, we employed the Cu12-NND-H electrode as a cathode to assemble one rechargeable Zn-nitrate battery that exhibits an impressive power density of 34.0 mW·cm-2, demonstrating its promising application in energy conversion and storage.

Programmable Self‐Assembly from Two‐Dimensional Nanosheets to Spiral, Twisted and Branched Nanostructures

AbstractSelf‐assembly of nanomaterials into hierarchical structure is of great interest to fabricate functional materials. However, programmable design of the assembled structures remains a great challenge. Herein, we reported a programmable self‐assembly strategy to customize the assembled structure. The self‐assembly strategy is designed to orderly transform the two‐dimensional (2D) Ca ions assembled F127 nanosheets (Ca‐F127 NSs) into spiral nanosheet structures (S‐Ca‐F127 NSs), branched nanosheet structures (B‐Ca‐F127 NSs), branched‐spiral nanosheet structures (B‐S‐Ca‐F127 NSs), and twisted‐branched structures (T‐Ca‐F127 NBs). Wide‐angle X‐ray scattering (WAXS) and X‐ray absorption spectroscopy (XAS) indicate that these different structures maintain the same orthorhombic phase and Ca‐O octahedral coordination structure. Selected area electron diffraction (SAED) in the double‐tilt liquid nitrogen cooling holder identifies the Eshelby twist in the twisted structures, demonstrating the spiral structure are formed by screw dislocation growth. Cryo‐electron microscopy (cryo‐EM) proves the oriented epitaxial growth in the B‐Ca‐F127 NSs. Furthermore, the formation mechanisms of spiral structure and branched structure can be recombined to form complex hierarchical structures. The epitaxial growth along screw dislocation can lead to the formation of B‐S‐Ca‐F127 NSs, while the twisted epitaxial growth in the screw dislocation can lead to the formation of T‐Ca F127 NBs.

Programmable Self-Assembly from Two-Dimensional Nanosheets to Spiral, Twisted and Branched Nanostructures.

Self-assembly of nanomaterials into hierarchical structure is of great interest to fabricate functional materials. However, programmable design of the assembled structures remains a great challenge. Herein, we reported a programmable self-assembly strategy to customize the assembled structure. The self-assembly strategy is designed to orderly transform the two-dimensional (2D) Ca ions assembled F127 nanosheets (Ca-F127 NSs) into spiral nanosheet structures (S-Ca-F127 NSs), branched nanosheet structures (B-Ca-F127 NSs), branched-spiral nanosheet structures (B-S-Ca-F127 NSs), and twisted-branched structures (T-Ca-F127 NBs). Wide-angle X-ray scattering (WAXS) and X-ray absorption spectroscopy (XAS) indicate that these different structures maintain the same orthorhombic phase and Ca-O octahedral coordination structure. Selected area electron diffraction (SAED) in the double-tilt liquid nitrogen cooling holder identifies the Eshelby twist in the twisted structures, demonstrating the spiral structure are formed by screw dislocation growth. Cryo-electron microscopy (cryo-EM) proves the oriented epitaxial growth in the B-Ca-F127 NSs. Furthermore, the formation mechanisms of spiral structure and branched structure can be recombined to form complex hierarchical structures. The epitaxial growth along screw dislocation can lead to the formation of B-S-Ca-F127 NSs, while the twisted epitaxial growth in the screw dislocation can lead to the formation of T-Ca F127 NBs.

How Does an Expert Artist Create Artwork? Skills and Strategies of an Expert Calligrapher Utilizing Ecological Constraints

How does an artist utilize ecological constraints to create artwork? What physical skills support this creative process? This paper presents three studies examining the bottom-up creative process of an expert calligrapher over 16 trials, analyzing the same case from different perspectives. The first study focuses on the calligrapher’s writing posture. It reveals that the calligrapher synchronized trunk and brush tip movements, flexibly altering whole-body coordination patterns depending on character forms. The second study investigates the modification process of the 17 characters written on the paper. The calligrapher progressively adjusted the form and layout of characters by establishing coordinative structures among the variables of character form and position, thus effectively utilizing the margins of the paper. The third study examines the calligrapher’s gaze searches. It shows that these searches allowed accurate adjustments of character shapes and layout by flexibly changing gaze direction distribution depending on the position of the paper and characters relative to the body. Collectively, the three studies demonstrate that the expert calligrapher’s key skill is the flexibility to make bottom-up adjustments to characters’ form and layout by actively utilizing the ecological constraints of the paper. This skill is supported by flexible gaze searches and a writing posture involving whole-body coordination.

Impact of Potassium Doping on a Two-Dimensional Kagome Organic Framework on Ag(111).

Alkali element doping has significant physical implications for two-dimensional materials, primarily by tuning the electronic structure and carrier concentration. It can enhance interface electronic interactions, providing opportunities for effective charge transfer at metal-organic interfaces. In this work, we investigated the effects of gradually increasing the level of K doping on the lattice structure and electronic properties of an organometallic coordinated Kagome lattice on a Ag(111) surface. With the introduction of K dopants into the 4-fold N-Ag coordinated Kagome lattice, the highly periodic Kagome lattice gradually tends to become discrete. Combining synchrotron radiation photoemission spectroscopy, scanning tunneling microscopy/spectroscopy, and density functional theory calculations, we revealed the mechanism of structural transformation of the lattice, i.e., the change in thermodynamically favored structures caused by competition of electron donors. As an electron donor with a lower ionization energy, K adatoms tend to replace the Ag adatoms and form a more thermodynamically stable N-K coordination structure. Moreover, enhanced charge transfer from K to the Kagome lattice induced a rigid shift of the Fermi level. Our investigation provides new insights for the study of alkali-doped organometallic nanostructures.

Precise manipulation of iron spin states in single-atom catalytic membranes for singlet oxygen selective production.

Heterogeneous single-atom catalysts are attracting substantial attention for selectively generating singlet oxygen (1O2). However, precise manipulation of atom coordination structures remains challenging. Here, the fine coordination structure of iron single-atom carbon-nitride catalysts (Fe-CNs) was manipulated by precisely tuning the heating rate with 1 °C min-1 difference. Multiple techniques in combination with density functional theory (DFT) calculations reveal that FeN6 coordination sites with high Fe spin states promote the adsorption, electron transfer, and dissociation of peroxymonosulfate (PMS), resulting in nearly 100% selection of 1O2 generation. A lamellar single atom catalytic membrane is constructed, exhibiting high permeance, high degradation, high-salinity resistance and sustained operation stability. This work provides ideas for regulating spin states of the metal site to fabricate catalysts with selective 1O2 generation for membrane separation and environment catalysis applications.

Excitation Wavelength Regulated Dynamic Luminescence in Bi/Sb co‐Doped Tin Halide for Encrypted Information Transmission and High‐Sensitivity Wavelength Sensor

AbstractThe coordination structure of Sb3+ within the host lattice critically influences its photophysical properties, sparking interest in luminescent metal halides with multiexciton emissions. Furthermore, the multi‐coordination lattice structure of Sb3+ dynamically emits light with excitation wavelength, highlighting the potential of Sb3+ ions in tuning luminescence and developing advanced optoelectronic materials. Herein, Sb3+ ions are successfully doped into Cs2SnCl6, and the obvious excitation wavelength‐dependent emission of Cs2SnCl6: Sb at room temperature is observed. To explain this phenomenon, density functional theory (DFT) calculations and time‐resolved spectra are conducted to confirm that the emission originated from two luminescence centers associated with the [SbCl6]3− and [SbCl5]2− coordination. Based on the tunable emission of Cs2SnCl6: Sb and the effective electron transfer between two triplet self‐trapped exciton states induced by Bi3+ and Sb3+, a pixelated code for information encryption is designed. The encoded patterns exhibit color changes under different UV wavelengths, enabling secure and straightforward information encryption. Furthermore, a sensitive UV wavelength sensor is prepared based on Cs2SnCl6: Bi/Sb, exploiting the monotonic relationship between chromaticity coordinates and wavelength, achieving a resolution superior to previously reported wavelength sensors. This study marks a substantial step toward advancing the multifunctional application of lead‐free metal halides.

Rational Design of Atomically Immobilized Fe‐N4 Sites via Acid‐Amine Chemistry: Leveraging Metal Ionic Assistance for Precise Morphology Control

ABSTRACTTailoring atomically dispersed single‐atom catalyst (Fe‐SAC) holding well‐defined coordination structure (Fe‐N4) along with precise control over morphology is a critical challenge. Herein, we propose a novel acid‐amine coupling reaction between metal‐chelated ionic liquid ([1‐(3‐aminopropyl) 3‐methylimidazolium tetrachloroferrate(III)] [APIM]+[FeCl4]−) and carboxylic groups of carbon allotropes (C = GO, CNT, CNF, and vX‐72) to precisely immobilize Fe‐Nx sites. Out of designed single‐atom catalyst (IL‐Fe‐SAC‐C), Fe‐N4 on graphene (IL‐Fe‐SAC‐Gr) delivered superior oxygen reduction reaction (ORR) activity by holding higher halfwave potential of 0.882 V versus RHE in 1.0 M KOH akin to Pt/C (0.878 V vs. RHE) and surpassing recently reported M–N–C catalysts with superior ethanol tolerance. Thanks to higher graphitization degree, enhanced surface characteristics, and richness in high‐density Fe‐N4 sites of IL‐Fe‐SAC‐Gr confirmed by XPS, X‐ray absorption spectroscopy (XAS), and HAADF analysis. The IL‐Fe‐SAC‐Gr catalyst‐coated cathode on testing in flexible direct ethanol fuel cells (f‐DEFC) delivered higher peak power density of 18 mW cm−2 by outperforming Pt/C‐based cathode by 3.5 times as a result of excellent ethanol tolerance. Further, the developed f‐DEFC successfully powered the Internet of Things (IoT)‐based health monitoring system. This method demonstrates novel strategy to tailor high‐performance single‐atom (Fe‐SAC‐C) sites on desired morphologies to meet specific application requirements with feasibility and versatility.