Single Atom Research Articles

Tailoring Single-Atom Coordination Environments in Carbon Nanofibers via Flash Heating for Highly Efficient Bifunctional Oxygen Electrocatalysis.

The rational design of carbon-supported transition metal single-atom catalysts necessitates precise atomic positioning within the precursor. However, structural collapse during pyrolysis can occlude single atoms, posing significant challenges in controlling both their utilization and coordination environment. Herein, we present a surface atom adsorption-flash heating (FH) strategy, which ensures that the pre-designed carbon nanofiber structure remains intact during heating, preventing unforeseen collapse effects and enabling the formation of metal atoms in nano-environments with either tetra-nitrogen or penta-nitrogen coordination at different flash heating temperatures. Theoretical calculations and in situ Raman spectroscopy reveal that penta-nitrogen coordinated cobalt atoms (Co-N5) promote a lower energy pathway for oxygen reduction and oxygen evolution reactions compared to the commonly formed Co-N4 sites. This strategy ensures that Co-N5 sites are fully exposed on the surface, achieving exceptionally high atomic utilization. The turnover frequency (65.33 s-1) is 47.4 times higher than that of 20 % Pt/C under alkaline conditions. The porous, flexible carbon nanofibers significantly enhance zinc-air battery performance, with a high peak power density (273.8 mW cm-2), large specific capacity (784.2 mAh g-1), and long-term cycling stability over 600 h. Additionally, the flexible fiber-shaped zinc-air battery can power wearable devices, demonstrating significant potential in flexible electronics applications.

Single‐Atom 3d Transition Metals on SnO2 as Model Cell for Conversion Mechanism: Revealing Thermodynamic Catalytic Effects on Enhanced Na Storage of Heterostructures

AbstractSince the discovery in 2000, conversion‐type materials have emerged as a promising negative‐electrode candidate for next‐generation batteries with high capacity and tunable voltage, limited by low reversibility and severe voltage hysteresis. Heterogeneous construction stands out as a cost‐effective and efficient approach to reducing reaction barriers and enhancing energy density. However, the second term introduced by conventional heterostructure inevitably complicates the electrochemical analysis and poses great challenges to harvesting systematic insights and theoretical guidance. A model cell is designed and established herein for the conversion reactions between Na and TMSA−SnO2, where TMSA−SnO2 represents single atom modification of eight different 3d transition elements (V, Cr, Mn, Fe, Co, Ni, Cu or Zn). Such a model unit fundamentally eliminates the interference from the second phase and thus enables independent exploration of activation manifestations of the heterogeneous architecture. For the first time, a thermodynamically dependent catalytic effect is proposed and verified through statistical data analysis. The mechanism behind the unveiled catalytic effect is further elucidated by which the active d orbitals of transition metals weaken the surface covalent bonds and lower the reaction barriers. This research provides both theoretical insights and practical demonstrations of the advanced heterogeneous electrodes.

Single-Atom 3d Transition Metals on SnO2 as Model Cell for Conversion Mechanism: Revealing Thermodynamic Catalytic Effects on Enhanced Na Storage of Heterostructures.

Since the discovery in 2000, conversion-type materials have emerged as a promising negative-electrode candidate for next-generation batteries with high capacity and tunable voltage, limited by low reversibility and severe voltage hysteresis. Heterogeneous construction stands out as a cost-effective and efficient approach to reducing reaction barriers and enhancing energy density. However, the second term introduced by conventional heterostructure inevitably complicates the electrochemical analysis and poses great challenges to harvesting systematic insights and theoretical guidance. A model cell is designed and established herein for the conversion reactions between Na and TMSA-SnO2, where TMSA-SnO2 represents single atom modification of eight different 3d transition elements (V, Cr, Mn, Fe, Co, Ni, Cu or Zn). Such a model unit fundamentally eliminates the interference from the second phase and thus enables independent exploration of activation manifestations of the heterogeneous architecture. For the first time, a thermodynamically dependent catalytic effect is proposed and verified through statistical data analysis. The mechanism behind the unveiled catalytic effect is further elucidated by which the active d orbitals of transition metals weaken the surface covalent bonds and lower the reaction barriers. This research provides both theoretical insights and practical demonstrations of the advanced heterogeneous electrodes.

Main-Group Elements Enhance Electrochemical Nitrogen Reduction Reaction of Vanadium-Based Single Atom Catalysts Through d-p Orbital Hybridization.

Developing active sites with flexibility and diversity is crucial for single atom catalysts (SACs) towards sustainable nitrogen fixation at ambient conditions. Herein, the effects of doping main group metal elements (MGM) on the stability, catalytic activity, and selectivity of vanadium-based SACs is systematically investigated based on density functional theory calculations. It is found that the catalytic activity of V site can be significantly enhanced by the synergistic effect between MGM and vanadium atoms. More importantly, a volcano curve between the catalytic activity and the adsorption free energy of NNH* can be established, in which V-Pb dimer embedded on N-coordinated graphene (VPb-NG) exhibits optimal NRR activity due to its location at the top of volcano. Further analysis of electronic structures reveals that the unoccupancy ratio (eg/t2g) of V site is dramatically increased by the strong d-p orbital hybridization between V and Pb atoms, subsequently, N2 is activated to a larger extent. These interesting findings may provide a new path for designing active sites in SACs with excellent performance.

Insight into mechanism for remarkable photocatalytic hydrogen evolution of Cu/Pr dual atom co-modified TiO2.

The development of high-activity photocatalysts is crucial for the current large-scale development of photocatalytic hydrogen applications. Herein, we have developed a strategy to significantly enhance the hydrogen photocatalytic activity of Cu/Pr di-atom co-modified TiO2 architectures by selectively anchoring Cu single atoms on the oxygen vacancies of the TiO2 surface and replacing a trace of Ti atoms in the bulk with rare earth Pr atoms. Calculation results demonstrated that the synergistic effect between Cu single atoms and Pr atoms regulates the electronic structure of Cu/Pr-TiO2, thus promoting the separation of photogenerated carriers and their directional migration to Cu single atoms for the photocatalytic reaction. Furthermore, the d-band center of Cu/Pr-TiO2, which is located at -4.70 eV, optimizes the adsorption and desorption behavior of H*. Compared to TiO2, Pr-TiO2, and Cu/TiO2, Cu/Pr-TiO2 displays the best H* adsorption Gibbs free energy (-0.047 eV). Furthermore, experimental results confirmed that the photogenerated carrier lifetime of Cu/Pr-TiO2 is not only the longest (2.45 ns), but its hydrogen production rate (34.90 mmol g-1 h-1) also significantly surpasses those of Cu/TiO2 (13.39 mmol g-1 h-1) and Pr-TiO2 (0.89 mmol g-1 h-1). These findings open up a novel atomic perspective for the development of optimal hydrogen activity in dual-atom-modified TiO2 photocatalysts.

Structurally optimized rosette-like microspheres carbon with Fe-Ni single atom sites for bifunctional oxygen electrocatalysis in Zinc-Air batteries

Developing a secure and effective bifunctional oxygen catalyst for the ORR and OER is still a significant obstacle in the design of rechargeable zinc-air batteries. Here, a hollow rose-shaped bifunctional electrocatalyst is synthesized with an sacrificial template strategy (FeNi-NC). X-ray absorption fine structure analysis reveals the FeNi-NC catalyst contains FeN4 and NiN4 active sites as well as FeNi3 alloy. This hollow, flower-like structure performs low density, large specific surface area, and high permeability. Its inner cavities not only provide additional triple-phase interfaces to accelerate the reduction and oxidation of O2, but also enhance the diffusion of reactants on the catalyst. By controlling the input of Fe and nickel metal salts, the dispersion of active sites can be effectively tuned. Owing to the large number of exposed active sites on the carbon nanosheets, the synthesized FeNi-NC catalysts exhibit high electrocatalytic activity in both ORR (E1/2 = 0.852 V) and OER (ηj=10 = 359 mV). The construction of rechargeable zinc-air batteries resulted in a high power density of 135.78 mW cm−2, a better specific capacitance of 726.9 Wh kgZn−1 and 210 h enduring durability. More importantly, density functional theory (DFT) calculations indicate that the electronic interactions between Fe/Ni and nitrogen-doped carbon matrices play a pivotal role in enhancing the electrocatalytic performance of functional groups. These interactions effectively disrupt the electronic neutrality of carbon atoms, thereby accelerating the kinetics of the reaction. This research provides a new method for the preparation of single atom catalysts with bifunctional activities.

Pt Single Atoms Loaded on Thin-Layer TiO2 Electrodes: Electrochemical and Photocatalytic Features.

Recently, the use of Pt in the form of single atoms (SA) has attracted considerable attention to promote the cathodic hydrogen production reaction from water in electrochemical or photocatalytic settings. First, produce suitable electrodes by Pt SA deposition on Direct current (DC)-sputter deposited titania (TiO2)layers on graphene-these electrodes allow to characterization of the electrochemical properties of Pt single atoms and their investigation in high-resolution HAADF-STEM. For Pt SAs loaded on TiO2, electrochemical H2 evolution shows only a very small overpotential. Concurrent with the onset of H2 evolution, agglomeration of the Pt SAs to clusters or nanoparticles (NPs) occurs. Potential cycling can be used to control SA agglomeration to variable-size NPs. The electrochemical activity of the electrode is directly related to the SA surface density (up to reaching the activity level of a plain Pt sheet). In contrast, for photocatalytic H2 generation already a minimum SA density is sufficient to reach control by photogenerated charge carriers. In electrochemical and photocatalytic approaches a typical TOF of ≈100-150 H2 molecules per second per site can be reached. Overall, the work illustrates a straightforward approach for reliable electrochemical and photoelectrochemical investigations of SAs and discusses the extraction of critical electrochemical factors of Pt SAs on titania electrodes.

Qualitative and quantitative electrochemiluminescence evaluation of trace Pt single-atom in MXenes

The analysis of trace Pt single-atom (SA) represents a significant challenge, given the crucial role of single-atom platinum (Pt) in energy storage and electrocatalysis. Here, we present an electrochemiluminescence (ECL) platform that enables the qualitative and quantitative analysis of trace Pt SA using luminol as the ECL luminophore. It is observed that different Pt species in Ti3-xC2Ty MXenes resulted in distinct reactive oxygen species (ROS) potentials for luminol cathodic electrochemiluminescence (ECL), achieved through distinctive oxygen reduction reaction (ORR) pathways, in which oxygen acts as the co-reactant. Furthermore, the cathodic luminol ECL intensity increases in proportion to the Pt atom content, thereby enabling quantitative analysis of trace Pt single atoms. The detection limit is 0.014 wt%, which is comparable to the current mainstream Pt SA quantification techniques. By utilizing this ECL method, it is possible to successfully evaluate both qualitatively and quantitatively the changes in Pt SA during the ORR processes. This ECL platform provides a valuable toolbox for the analysis of Pt SA catalysts and for the evaluation of the mechanisms involved in electrocatalysis applications.

Theoretical study on the electrochemical CO2 reduction performance of MoS2-supported Ni single atoms with transition metal substrate doping

In the context of increasing energy issues and climate change, the development of electrochemical CO2 reduction strategies using single atom catalysts (SACs) presents a viable solution by converting CO2 into high-value-added products. Transition metal dichalcogenides (TMDs) have emerged as the main candidates for SACs in electrocatalytic CO2 reduction reaction (CO2RR) catalysts. The regulation of the second coordination sphere of SACs is known to modulate their electronic structure and catalytic behavior. This study delves into the effect of transition metal-doped substrates on SACs. We employed spin-polarization density functional theory (DFT) to design a series of Ni/TM-MoS2 monolayer MoS2 materials, with transition metals (including Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt and Au) substituting the Mo atoms and anchoring single atom Ni. Among them, six Ni/TM-MoS2 catalysts doped with Mn, Fe, Co, Ru, Rh, and Ir demonstrate enhanced CO2RR activity and selectivity when compared to unmodified Ni/MoS2. The Ni/Ru-MoS2 SAC exhibits the best catalytic activity and selectivity for formic acid production, with a limiting potential (UL) of -0.06 V. The incorporation of the metal-doped substrate lowers the work function of the catalyst, facilitating electron transfer and reaction progression. Furthermore, a volcanic relationship was observed between the work function and UL. This study provides strategic insights into the design and development of SACs, highlighting the potential for future modifications and applications.

Nickel-based dual single atom electrocatalysts for the nitrate reduction reaction

Electrochemical nitrate (NO3−) reduction reaction (NO3−RR) to ammonium (NH4+) or nitrogen (N2) provides a green route for nitrate remediation. However, nitrite generation and hydrogen evolution reactions hinder the feasibility of the process. Herein, dual single atom catalysts were rationally designed by introducing Ag/Bi/Mo atoms to atomically dispersed NiNC moieties supported by nitrogen-doped carbon nanosheet (NCNS) for the NO3−RR. Ni single atoms loaded on NCNS (Ni/NCNS) tend to reduce NO3− to valuable NH4+ with a high selectivity of 77.8 %. In contrast, the main product of NO3−RR catalyzing by NiAg/NCNS, NiBi/NCNS, and NiMo/NCNS was changed to N2, giving rise to N2 selectivity of 48.4, 47.1 and 47.5 %, respectively. Encouragingly, Ni/NCNS, NiBi/NCNS, and NiAg/NCNS showed excellent durability in acidic electrolytes, leading to nitrate conversion rates of 70.3, 91.1, and 93.2 % after a 10-h reaction. Simulated wastewater experiments showed that NiAg/NCNS could remove NO3− up to 97.8 % at −0.62 V after 9-h electrolysis. This work afforded a new strategy to regulate the reaction pathway and improve the conversion efficiency of the NO3−RR via engineering the dual atomic sites of the catalysts.

Micromechanism of the effect of coal functional groups on the catalytic/esterification reaction of acetic acid

Acidification modification has proven to be a successful approach for enhancing the permeability of low-permeability coal seams and increasing coalbed methane extraction. To explore the influence of acetic acid on the organic structure of coal, a combined approach of experimental research and quantum chemical calculation is employed to examine the reaction mechanism of coal organic structure in response to acetic acid. Fourier transform infrared spectroscopy reveals a reduction in the content of hydroxyl and C–O bonds in the treated samples, along with the appearance of an absorption peak of C=C bonds. This demonstrates that the main site of acetic acid acidification modification on coal molecules is the hydroxyl functional group. Therefore, glycerol can be used as a simplified model of coal molecules for further investigation. In addition, three typical functional groups (phenyl, hydroxyl, amino) are selected as the research objects. The electronic density topological properties, molecular surface electrostatic potential, Mayer bond orders and CM5 charge of coal molecules were calculated based on quantum chemical theory. This reveals the intrinsic strength of each chemical bond between single atoms in a molecule, thereby predicting potential reaction pathways between acetic acid and coal molecules. The micro-mechanism of acetic acid catalyzing/esterifying the organic structure of coal is studied using transition state methods. The computational results show that there are two main modes of reaction between acetic acid and coal molecules: (1) acetic acid catalyzes the dehydration reaction of coal molecules; (2) acetic acid reacts with coal molecules to form ester intermediates, followed by decomposition through various reactions. Among the 14 reaction pathways, acetic acid provides protons or groups to trigger the dehydration of coal molecules. Interestingly, it is found that the overall hydroxyl group participates in the reaction is easier than the individual hydrogen atom on the hydroxyl group, and the overall carboxyl group participates in the reaction is easier than the individual hydroxyl group. This indicates that the higher the overall atomic reactivity of acetic acid, the lower the reaction barrier. Compared with catalytic reactions, acetic acid tends to undergo esterification reactions with hydroxyl groups, with the phenyl ring functional group significantly affecting the reaction barrier. The introduction of various oxygen-containing functional groups like ketone, aldehyde, and ester in the reaction products will hinder the adsorption of non-polar methane, reduce the adsorption capacity of coal seams for gas, and play an essential role in promoting gas desorption. The research findings can provide theoretical guidance for the organic acidification modification of low-permeability coal seams to enhance gas permeability and coalbed methane extraction.

Synergistic Cu Single Atoms and MoS2‐Edges for Tandem Electrocatalytic Reduction of NO3− and CO2 to Urea

AbstractUrea electrosynthesis from co‐electrolysis of NO3− and CO2 (UENC) under ambient conditions is recognized as an appealing approach for effective and sustainable urea production, while it requires high‐efficiency UENC electrocatalysts to promote the C─N coupling and hydrogenation processes. Herein, single‐atom Cu anchored on MoS2 (Cu1‐MoS2) is explored as a highly active and selective UENC catalyst. Theoretical calculations and operando spectroscopic characterizations unveil the synergistic tandem catalysis of Cu1‐MoS2 for the UENC, where Cu single atoms trigger the early C─N coupling, while MoS2‐edges promote the key hydrogenation step of *CO2NH2 to *COOHNH2 for urea generation. Strikingly, Cu1‐MoS2 equipped in a flow cell achieves the excellent UENC performance with a maximum urea‐Faradaic efficiency of 57.02% at −0.6 V and the corresponding urea yield rate of 23.3 mmol h−1 g−1, surpassing nearly all previously reported UENC catalysts.

Potent and Protease Resistant Azapeptide Agonists of the GLP-1 and GIP Receptors.

The gut-derived peptide hormones glucagon-like peptide-1 (GLP-1) and glucose-dependent insulinotropic polypeptide (GIP) play important physiological roles. Stabilized agonists of the GLP-1 receptor (GLP-1R) and the GIP receptor (GIPR) for the management of diabetes and obesity have generated widespread enthusiasm and have become blockbuster drugs. These therapeutics are refractory to the action of dipeptidyl peptidase-4 (DPP4), that catalyzes rapid removal of the two N-terminal residues of the native peptides, in turn severely diminishing their activity profiles. Here we report that a single atom change from carbon to nitrogen in the backbone of the entire peptide make them refractory to DPP4 action while still retaining full potency and efficacy at their respective receptors. This was accomplished by use of aza-amino acids, that are bioisosteric replacements for a-amino acids that perturb the structural backbone and local side chain conformations. Molecular dynamics simulations reveal that aza-amino acid can populate the same conformational space that GLP-1 adopts when bound to the GLP-1R. The insertion of an aza-amino acid at the second position from the N-terminus in semaglutide and in a dual agonist of GLP-1R and GIPR further demonstrates its capability as a viable alternative to current DPP4 resistance strategies while offering additional structural variety.

The Mechanism of Heterogeneous Ice Nucleation by Fatty Alcohol Monolayers.

Organic ice nucleating substances (INSs) are thought to play an essential role in cloud formation and, hence, precipitation and climate. Organic INSs are an important but poorly understood class of INSs in the atmosphere. To study organic INSs with exposed hydroxylated surfaces, researchers have previously used fatty alcohol monolayers as model systems. For alcohol monolayers, ice nucleation temperatures increase with increasing alkyl chain length and show a high-low oscillation following the number (odd-even) of carbon atoms in the alkyl chains. We employ atomistic models, together with molecular dynamics simulations, to investigate ice nucleation by C20H41OH, C30H61OH, and C31H63OH monolayers. As expected, we find that ice nucleation by alcohol monolayers depends on the lattice match to ice, and a poorer lattice match can at least partially account for the reduced ice nucleation ability of C20H41OH monolayers compared to monolayers of the longer chain alcohols. More interestingly, our simulations identify a limited range of alcohol configurations that readily nucleate ice via the basal plane. For configurations outside this range, ice nucleation did not occur on the time scale of our simulations (i.e., 5000 ns). The configurational feature that crucially influences ice nucleation is the angle between the alcohol C-O bond and the interfacial plane. C-O bonds directed sharply toward or away from the water phase strongly inhibit ice nucleation. In contrast, ice nucleation is easily observed for a relatively narrow band of C-O bond orientations centered about the surface plane. For comparable surface configurations, the ice nucleating abilities of C30H61OH and C31H63OH monolayers are practically identical, but the existence of a narrow band of ice-compatible surface configurations can perhaps explain why odd-chain alcohol monolayers are better INSs than even-chain alcohol monolayers. Earlier simulations have shown that for alcohols differing by a single carbon atom, the odd-chain monolayer is less rigid than the even-chain monolayer. This suggests the possibility that for odd-chain alcohol monolayers, the orientation of the C-O bonds can more easily adjust into the ice-compatible range than their even-chain counterparts, accounting for their enhanced ice nucleating ability.

Imaging Negative Charge around Single Vanadium Dopant Atoms in Monolayer Tungsten Diselenide Using 4D Scanning Transmission Electron Microscopy.

There has been extensive activity exploring the doping of semiconducting two-dimensional (2D) transition metal dichalcogenides in order to tune their electronic and magnetic properties. The outcome of doping depends on various factors, including the intrinsic properties of the host material, the nature of the dopants used, their spatial distribution, as well as their interactions with other types of defects. A thorough atomic-level analysis is essential to fully understand these mechanisms. In this work, the vanadium-doped WSe2 monolayer grown by molecular beam epitaxy is investigated using four-dimensional scanning transmission electron microscopy (4D-STEM). Through center-of-mass-based reconstruction, atomic-scale maps are produced, allowing the visualization of both the electric field and the electrostatic potential around individual V atoms. To provide quantitative insights, these results are successfully compared to multislice image simulations based on ab initio calculations, accounting for lens aberrations. Finally, a negative charge around the V dopants is detected as a drop in the electrostatic potential, unambiguously demonstrating that 4D-STEM can be used to detect and to accurately analyze single-dopant charge states in semiconducting 2D materials.

Ferroptosis Therapy of Colorectal Cancer by Single Co Atom Supported on Fe-Based Zeolitic Imidazolate Frameworks

Ferroptosis Therapy of Colorectal Cancer by Single Co Atom Supported on Fe-Based Zeolitic Imidazolate Frameworks

Activation of H2O2 using a single-atom Cu catalyst for efficient tetracycline degradation

The abuse of antibiotics has caused serious harm to the ecological environment and human health. Fenton-like advanced oxidation technology is a green and effective treatment means, but how to improve the Fenton reaction efficiency and wide pH adaptability is still a big challenge. Herein, we designed and developed a single-atom catalyst Cu1-CN with graphite-phase carbon nitride as the carrier by loading a low amount of metal Cu. The N atom anchors the copper atom in the form of a coordination bond, and the single atom Cu site has excellent performance in activating H2O2. Not only a short period of time (10 min) oxidation degradation of tetracycline (degradation rate 80 %), and in a broad range of pH (3.2 ∼ 9.5) still maintaining high removal performance (efficiency more than 70 %). Combined with X-ray absorption fine structure characterization and density functional theory (DFT) calculations, it is considered that isolated Cu atom and N atom cooperate to construct highly reactive Cu-N4 active centre, which completes the task of H2O2 activation. This study provides a new theoretical basis and technical support for the degradation of antibiotic pollutants by single-atom Fenton-like reaction.

Co(III), Co(II), Co(I): Tuning Single Cobalt Metal Atom Oxidation States in a 2D Coordination Network

AbstractIt is shown that the self‐assembly of a surface‐confined metal–organic network such as cobalt porphyrins on graphene is accompanied by the evolution of coordination‐dependent observables in the electronic structure: variation of the layer's valence states within almost 1 eV range and of the metal atoms oxidation states. Coordination of cobalt porphyrins, driven by Co ad‐atoms, allows the synthesis of single metal atom centers with +3, +2, or +1 oxidation states. The electronic structure is determined by lateral interactions extending up to a few nanometers, beyond nearest‐neighbor distances. The reactivity of the single Co sites, which is strongly dependent on the local electronic configuration and, thus, on the metal‐specific oxidation state, is probed by carbon monoxide, which is found to ligate at pyridinic Co(I) at room temperature for background pressures above a fraction of a mbar.

Measuring the Magnetic Anisotropy of Metal-Metal Multiple Bonds: The Importance of Correcting for Ligand Effects.

We describe the synthesis and characterization of the quadruply-bonded dimer Mo2(CH2NMe2BH3)4 in which each molybdenum(II) center is bound to two chelating boranatodimethylaminomethyl (BDAM) ligands. The BDAM anions bind to the metal at one end by a metal-carbon σ bond and at the other by a three-center M-H-B interaction. Each BDAM ligand chelates to a single Mo atom so that the metal-metal bond is unbridged; the Mo-Mo distance is 2.114(2) Å. Structural and solution NMR data, analyzed via McConnell's equation and supported by DFT calculations, show that the magnetic anisotropies associated with highly polarizable and π-bonding ligands (such as chloride groups and aryl rings) can greatly affect the NMR chemical shifts of reporter groups, so that ignoring their contributions leads to significant overestimates of the anisotropy due just to the metal-metal bond. We propose a method to quantify and correct for the magnetic anisotropy effects arising from the ligands. Application of this method to Mo2(BDAM)4 indicates that the magnetic anisotropy of the Mo-Mo quadruple bond in this molecule is about -800 × 10-36 m3 molecule-1. Anisotropies significantly higher than this value (as sometimes reported in the prior literature) are most likely incorrect.

Anchoring Metal-Nitrogen Sites on Porous Carbon Polyhedra with Highly Accessible Multichannels for Efficient Oxygen Reduction.

Transition metal-nitrogen-carbon complexes, featuring single metal atoms embedded in a nitrogen-doped carbon matrix, emerge as promising alternatives to traditional platinum-based catalysts, offering cost-effectiveness, abundance, and enhanced catalytic performance. This work introduces a novel method for the etching and doping of zeolitic imidazolate frameworks (ZIFs) with transition metals, creating a uniform distribution of secondary metal centers on ZIF surfaces. By disrupting the crystalline symmetry of ZIFs through synthetic defect engineering, we gain access to their entire internal volume, creating multichannel pathways. The absorption of metal ions is theoretically simulated, demonstrating their thermodynamically spontaneous nature. The selective removal of defect channels under Lewis acidic conditions, induced by metal ion alcoholysis/hydrolysis, facilitates the introduction of metal atoms into ZIF cavities. The resulting single-atom catalyst, after pyrolysis, features a three-dimensional (3D) multichannel structure, high surface area, and uniformly dispersed metal atoms within the N-doped carbon matrix, establishing it as an exceptional catalyst for the oxygen reduction reaction (ORR). Our findings highlight the potential of using metal etching in defect-engineered metal-organic frameworks (MOFs) for single-atom catalyst preparation, paving the way for the next generation of high-performance, cost-effective ORR catalysts in sustainable energy systems.