Metal Atoms Research Articles

DFT modeling of reaction of H2 with O2 pre-adsorbed on In2O3(011) surface

The DFT approach is used for the first time to model the reaction of hydrogen with oxygen molecule adsorbed on the defective surface of In2O3(011). This reaction is crucial for hydrogen detection by In2O3 sensor. The activation energies are calculated using two mechanisms involving the formation of both an adsorbed water molecule and hydroxyl groups on the In2O3(011) surface. One hydroxyl group is formed due to the bonding of OH with the surface metal atom, and the other due to the bonding of hydrogen with oxygen of the lattice. Both reactions are characterized by the presence of a potential barrier and are exothermic. The activation energies of the two reactions are calculated by the climbing-image nudged elastic band method to be 0.99 eV and 0.98 eV. The results of the calculations are compared with available experimental data. It is also shown that the presence of a surface neutral oxygen vacancy leads to the formation of a vacancy state below the Fermi level, and the electron density is concentrated on the fourfold coordinated indium atom.

Basics of the reaction kinetics on metallic alloys.

Kinetics of heterogeneous catalytic reactions are often complicated by various factors, and from the perspective of statistical physics the development of the corresponding models is frequently challenging especially in the case of practically important alloy catalysts. To extend the basics in this area, I use a generic kinetic model of N_{2} formation inthe NO reaction with such species as CO or H_{2}. The focus is onthe reaction on the surface of a bimetallic alloy with low integral fraction of one of the metals so that the alloy is formed only at the surface. The main goal is to illustrate the specifics of the reaction kinetics and to clarify the accuracy of various approximations which are often inevitable for the analysis of such systems. The key results are as follows. (i) In the baseline one-metal case with the Langmuir-type equations, the model predicts the existence of the optimal adsorbate binding energy corresponding to the maximal reaction rate. (ii) With suitable substitution of the symbols, the equations employed for a uniform surface [item (i)] can be used for the mean-field description of reaction on the surface of a random alloy. In particular, the maximum in the dependence of the reaction rate on the binding energy is converted to the maximum with respect to the alloy composition. (iii) The reaction kinetics on the random-alloy surface have been described exactly. The corresponding maximum in the reaction rate is lower and somewhat smeared compared to that predicted in the mean-field approximation for an alloy or for the optimal monometallic catalyst. (iv) The reaction kinetics have been scrutinized also in the case of two-dimensional (2D) segregation of metal atoms at the surface in the limits of slow and rapid adsorbate diffusion between the spots. The kinetics are shown to be qualitatively different in these limits and also compared to the random-alloy case. (v) The thermodynamic criteria for 2D segregation of metal atoms at the surface have been derived as well.

Synthesis, structural elucidation, and antibacterial activities of novel copper(II), cobalt(II), and nickel(II) complexes with a bidentate Schiff base ligand against pathogenic bacteria

Novel Schiff base metal complexes diaqua(4-chloro-2-{[(4-(dimethylamino)phenyl)methylene]amino}phenolato)M(II) ion, (M = copper/cobalt/nickel) have been synthesized using the ligand 4-chloro-2-((4-(dimethylamino)benzylidene)amino)phenol, which was prepared by reacting 2-amino-4-chlorophenol with 4-(dimethylamino)benzaldehyde in a molar ratio of 1:1. The synthesized compounds were characterized based on elemental analysis, FTIR, UV–vis., 1H and 13C NMR, powder XRD, mass spectrometry and magnetic studies. Spectroscopic investigations demonstrated that the metal atom coordinates to a bidentate Schiff base ligand via the azomethine nitrogen and phenolic oxygen. The appropriate molecular geometry for each metal complex has been proposed through the analysis of spectroscopic and analytical data, Specifically, tetrahedral geometry has been proposed for Co(II), Ni(II), and square planar geometry for Cu(II) complex. Theoretical calculations employing Density Functional Theory (DFT) validated the experimental results, elucidating optimized geometries, frontier molecular orbitals, natural bond orbital distributions, molecular electrostatic potentials, non-linear optical properties, IR vibrational modes, and UV absorbance profiles. Additionally, the compounds' biological efficacy was validated through molecular docking against receptors for Gram(+ve) bacteria, Bacillus subtilis (PDB ID: 5H67), Staphylococcus aureus (PDB ID: 3TY7) and Gram(-ve) bacteria, Escherichia coli (PDB ID: 3T88), Proteus vulgaris (PDB ID: 5I39). The outcome revealed that Co(II) complex exhibited highest binding energy with Escherichia coli and Bacillus subtilis while the ligand with Proteus vulgaris (5I39) and Staphylococcus aureus (3TY7). Further the study was extended to the MD Simulation in water for 100 ns to evaluate the binding affinities and its stabilities by analyzing the deviation, fluctuations, and intermolecular interactions. The research presented here showcase the potential of employing a Schiff base ligand and its Co(II) complex in the synthesis of novel, highly potent antibacterial agents to combat emerging diseases, which holds considerable importance in the field of pharmaceutical science—however, in-vitro studies are needed to validate the results.

Mining Knowledge from Crystal Structures of Homoleptic Complexes: Oxidation States of Metal Atoms

Mining Knowledge from Crystal Structures of Homoleptic Complexes: Oxidation States of Metal Atoms

Synthesis, characterization and investigation of biological activities of Schiff base and its Ni(II) complex obtained from 2-Benzoylpyridine and 3-Hydroxy-2-naphthoic hydrazide

In this paper, a new aryl hydrazone and its Nickel (II) complex were synthesized from 2-benzoylpyridine and 3-Hydroxy-2-naphthoic hydrazide. The synthesized compounds were characterized by elemental analysis, UV Vis., IR, NMR spectral studies and mass spectra. The data indicate that the metal atom is coordinated by the two ligands and that the [NiL2] complex is octahedral. The ligand is coordinated through carbonyl-O, azomethine-N, and pyridyl-N atoms. When tested against various reference bacterial strains and clinical isolates, it was discovered that the antibacterial activity of the [NiL2] complex was more effective than the ligand.

Realization of controlled Remote implementation of operation

Controlled remote implementation of operation (CRIO) enables to implement operations on a remote state with strong security. We transmit implementations by entangling qubits in photon-cavity-atom system. The photons transferred in fiber and the atoms embedded in optical cavity construct CZ gates. The gates transfer implementations between participants with the permission of controller. We also construct nonadiabatic holonomic controlled gate between alkali metal atoms. Decoherence and dissipation decrease the fidelity of the implementation operators. We apply anti-blockade effect and dynamical scheme to improve the robustness of the gate.

Laser driven generation of single atom Fe-N-C catalysts for the oxygen reduction reaction

Single-Atom Catalysts (SACs) have emerged as the ultimate solutions in challenging systems bridging the gap between homogeneous and heterogeneous catalysts. However, feasible synthesis methods are necessary to stabilize single metal atoms, increase catalyst loadings and scale up the synthesis. Due to its sluggish kinetics, the oxygen reduction reaction (ORR) is the main source of irreversibility in proton exchange membrane fuel cells (PEMFC). The most promising candidates to replace Pt-based catalysts for the ORR in fuel cells are the so-called Fe-N/C catalysts. These catalysts display high ORR activity in acidic and alkaline electrolytes. In this work, we propose a laser-driven pyrolysis approach to generate Fe-N/C SACs that involves decomposition of aerosolized iron-phthalocyanines. The resulting catalyst displays ORR activity in acidic and alkaline electrolytes, with competitive half-potential and kinetic current density values in comparison with state-of-the-art electrocatalysts.

Electroreduction of nitrate to ammonia on graphyne-based single-atom catalysts by combined density functional theory and machine learning study

Nitrate pollution has emerged as a significant global issue, prompting increased interests in electrocatalytic reduction of nitrate to ammonia (NO3RR). This study explores the use of graphyne as the substrate to anchor single transition metal (TM) atoms from the 3d and 4d series on acetylene corners, creating single-atom catalysts (SAC) for the NO3RR reaction. Two catalysts, CrGY and MoGY, were finally identified as promising catalysts for NO3RR with low limiting potential and high selectivity for NH3. To further investigate the origin of catalyst activity, in addition to traditional electronic structrue analysis, machine learning models of the least solution shrinkage and selection operator (LASSO), the sure independence screening and sparsifying operator (SISSO) and the gradient boosting regression (GBR) algorithm are adopt to reveal the intrinsic properties of catalysts that determine the NO3RR performance. After preliminary evaluation of the 13 prepared features with LASSO algorithm, GBR models revealed that the nitrate adsorption free energy ΔGNO3- and the NO bond length are the two most important descriptors for NO3RR performance. A general equation for the relationship between the limiting potential and the characteristics of the catalysts are obtained by SISSO model. Finally, with the assitance of combined density functional calculations and machine learning, this study provides new enlightening insights into practical application of graphyne as SACs for NO3RR.

Computational Engineering of Non-van der Waals 2D Magnetene for Enhanced Oxygen Evolution and Reduction Reactions.

Non-van der Waals two-dimensional materials containing exposed transition metal atoms are promising catalysts for green energy storage and conversion. For instance, hematene and ilmenene have been successfully applied as catalysts. Building on these reports, this work is the first investigation of recently synthesized magnetene towards the Oxygen Evolution Reaction (OER) and Oxygen Reduction Reaction (ORR). Using Density Functional Theory (DFT) calculations, we unveil the mechanism, performance and ideal conditions for OER and ORR on magnetene. With overpotentials of ηOER = 0.50 V and ηORR = 0.41 V, the material is not only a bifunctional catalyst, but also superior to state-of-the-art systems such as Pt and IrO2. Additionally, its catalytic properties can be further enhanced through engineering strategies such as point defects and in-plane compression. It reaches ηORR = 0.28 V at a compressive strain of only 2%, while the presence of Ni boosts it to ηOER = 0.39 V and ηORR = 0.31 V, comparable to many reported single-atom catalysts. Overall, this work demonstrates that magnetene is a promising bifunctional catalyst for applications such as regenerative fuel cells and metal-air batteries.

Mechanistic Insight of High-Valent First-Row Transition Metal Complexes for Dehydrogenation of Ammonia Borane.

Designing an efficient and cost-effective catalyst for ammonia borane (AB) dehydrogenation remains a persistent challenge in advancing a hydrogen-based economy. Transition metal complexes, known for their C-H bond activation capabilities, have emerged as promising candidates for AB dehydrogenation. In this study, we investigated two recently synthesized C-H activation catalysts, 1 (CoIV-dinitrate complex) and 2 (NiIV-nitrate complex), and demonstrated their efficacy for AB dehydrogenation. Using density functional theory calculations and a detailed analysis, we elucidated the AB dehydrogenation mechanism of these complexes. Our results revealed that both complexes 1 and 2 can efficiently dehydrogenate AB at room temperature, although the abstraction of molecular H2 from these complexes requires slightly elevated temperatures. We utilized H2 binding free energy calculations to identify potentially active sites and observed that complex 2 can release two equivalents of H2 at a temperature slightly higher than room temperature. Furthermore, we investigated AB dehydrogenation kinetics and thermodynamics in iron (Fe)-substituted systems, complexes 3 and 4. Our results showed that the strategic alteration of the central metal atom, replacing Ni in complex 2 with Fe in complex 4, resulted in enhanced kinetics and thermodynamics for AB dehydrogenation in the initial cycle. These results underscore the potential of high-valent first-row transition metal complexes for facilitating AB dehydrogenation at room temperature. Additionally, our study highlights the beneficial impact of incorporating iron into such mononuclear systems, enhancing their catalytic activity.

Superlight Ambient Temperature Reversible Hydrogen Storage Media Based on Alkali and Alkali Earth Metal-Functionalized 2D Square-Octagon BCN Monolayer.

Energy has always been the engine of human beings; however, because of the environmental pollution caused by traditional fossil fuels, the development of more sustainable energy resources is urgently needed. The hydrogen storage medium is essential for its realization. Here, we introduce a hydrogen storage material, a two-dimensional (2D) square-octagon BCN (SO-BCN) monolayer, composed of lightweight elements (B, C, and N) and strategically functionalized with alkali and alkali earth metal atoms (Li, Na, Mg, and K). Notably, Li@SO-BCN and Mg@SO-BCN exhibit exceptional reversible hydrogen storage capabilities, surpassing the DOE standard of 5.5 wt %, with gravimetric capacities of 7.129 wt % and an impressive value of 11.656 wt %, alongside low adsorption energies of -0.21 eV/H2 and -0.268 eV/H2 at room temperature, respectively. Our investigation, which combines analysis of the atomic structure, electronic structure, and hydrogen process, reveals distinct mechanisms at play: Li activates the substrate, creating additional adsorption sites on the SO-BCN monolayer. Compared with Li, the functionalization of Mg atoms not only activates SO-BCN via charge transfer but also allows Mg2+ to act as a potent attractor for H2 molecule adsorption. This work provides both promising candidates for future hydrogen storage media based on 2D monolayers and a design paradigm for next-generation hydrogen storage materials, emphasizing the synergy of electron-donating species, substrate activation, and hierarchical porous structures.

Scaling Up Stability: Navigating from Lab Insights to Robust Oxygen Evolution Electrocatalysts for Industrial Water Electrolysis

AbstractIn the pursuit of sustainable hydrogen production via water electrolysis, paramount importance of electrocatalyst stability emerges as a defining factor for long‐term industrial viability. A thorough understanding and enhancement of stability not only ensure extended catalyst lifetimes but also pave the way for consistent and efficient hydrogen generation. This review focuses on the pivotal role of stability in determining the practical viability of oxygen evolution electrocatalysts (OECs) for large‐scale applications in water electrolysis for hydrogen production. The paper explores the pivotal role of stability over initial activity, citing examples and hypothetical scenarios. First, figures of merits for stability evaluation of the electrocatalyst are explained along with the available benchmarking protocols for stability evaluation. Further, the text delves into various strategies that can enhance the stability of the electrocatalyst which include self‐healing/regeneration pathway, oxygen evolution reaction (OER) mechanism optimization to achieve highly stable OER and stabilization of active metals atoms within the electrocatalyst to inhibit dissolution as a way forward for industrial application. The interplay of stability, activity, and cost is also explained to suit the industrial application of the electrocatalyst. Lastly, it outlines challenges, prospects, and future directions, presenting a guide for advancing OECs in the hydrogen generation landscape.

Rational design of Co sub-nano clusters by electronic metal-support interaction for inducing Li2O2 growth

The cathodic electrocatalyst for Li-O2 battery with rich and effective active sites was significant to optimize the formation and decomposition of Li2O2, improve the discharge-charge kinetics. Herein, we develop a novel strategy to controllably prepare sub-nano clusters modified carbon materials. The sub-nano cluster of Co was anchored on the Ketjen Black (KB) substrate and achieved electrocatalytic performance promotion via rational design of the electronic metal-support interaction (EMSI), where the numerous sites in KB with large specific area and geometric space were activated. The experimental and theoretical results indicated that the substrate of the carbon plane could be strongly coupled with the metal atoms and optimized the electronic structure of carbon, leading to effective tuning for Li2O2 growth. The composite exhibited superior performance with high specific capacity of 15311 mAh g−1, low overpotential of 0.88 V and long-term durability of more than 140 cycles with 1000 mAh g−1, strongly related with the optimized Li2O2 growth and decomposition in battery operation. It provides a new strategy for novel electrocatalyst design to tuning the Li2O2 related process.

Construction of a Boron Chain on a Single Metal by Dehydrocoupling of Borane Ligands.

Borane coordination, B-H borane bond activation, and borane catenation via metal-mediated dehydrocoupling to form electron-precise B-B bonds are reported. The reaction of trans-[M(IMes)2Cl4] (M = W, Mo) (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) with borates Li[BH3R] (R = Mes, Dur; Mes = 2,4,6-Me3C6H2 and Dur = 2,3,5,6-Me4C6H) afforded the complexes [M(IMes)(η2-H2BR)2(η1-H2BR)] (M = W: R = Mes 1, R = Dur 3; M = Mo: R = Mes 2, R = Dur 4). Three borane ligands are coordinated in 1-4 to the group 6 metal atom via five (σ-B-H) bonds. Reaction of 1 with the phosphines PMe3 and PEt3, respectively, led to the elimination of one of the borane ligands and afforded the hydrido (σ-B-H)-boryl bis(σ-B-H)-borane complexes trans-[W(IMes)(PR3)(η1-HBMes)(η2-H2BMes)(H)] (R = Me 5, R = Et 6), in which the metal atom inserted into one of the remaining σ-B-H bonds of the borane ligands. Reaction of 1 with an additional equivalent borane BH2Mes resulted in borane dehydrocoupling and formation of complex [W(IMes)(η4-BH2Mes-BMes-BMes-BH2Mes)] 7, featuring a unique B4 chain as a ligand. Reaction of trans-[W(IMes)2Cl4] with NaBH4 also led to B-B coupling, and the metallaborane cluster [{W(IMes)(BH4)}2(B5H9)] 9 was formed, in which two tungsten atoms bridge a B5 chain.

Engineering the electronic and magnetic properties of monolayer TiS[formula omitted] through systematic transition-metal doping

Despite substantial interest, most of the two-dimensional (2D) materials are not magnetic in their pristine form. Several standard approaches, such as adsorption of atoms, introduction of point defects, and edge engineering, have been developed to induce magnetism in two-dimensional materials. In this way, we investigate the electronic and magnetic properties of monolayer TiS2 doped with 3d transition metals (TMs) atoms in both octahedral 1T and trigonal prismatic 1H structures using first-principles calculations. In its pristine form, TiS2 is a non-magnetic semiconductor. The bands near the Fermi energy primarily exhibit d orbital characters, and due to the presence of ideal octahedral and trigonal arrangements, they are well separated from other bands with p character. Upon substituting 3d-TM atoms in both structures, a variety of electronic and magnetic phases emerge, including magnetic semiconductor, magnetic half-metal, and magnetic metal. Chromium exhibits the largest magnetic moment in both the 1T and 1H structures. The 1T structure shows a slightly higher magnetic moment of 3.4 μB compared to the 1H structure 3.1 μB, attributed to the distorted octahedral structure of the 1T structure. Unlike pristine TiS2, the deficiency in saturation of neighboring S atoms in the presence of impurities leads to the proximity of energy levels of d and p states, resulting in unexpectedly sizeable magnetic moments. Another interesting case is Cobalt, which leads to a magnetic moment of approximately 0.8 μB in the 1H structure, while the Co exhibits a non-magnetic state in the 1H structure. These materials demonstrate a high degree of tunability and can be optimized for various magnetic applications.

Theoretical study of tandem catalysts based on metal porphyrin-phthalocyanine two-dimensional carbon-rich conjugated frameworks for the co-reduction of NO3− and CO2 in the electrosynthesis of methylamine

Electrocatalytic NO3− and CO2 co-reduction to synthesize methylamine can remove NO3− and CO2 pollutants and produce valuable methylamine. However, the catalytic mechanism of electrocatalytic NO3− and CO2 co-reduction for the synthesis of methylamine is not sufficiently understood, and this research remains challenging. To supply the catalytic mechanism needed to create effective electrocatalysts, we systematically investigated the performance of metal-extended phthalocyanine and metalloporphyrin tandem catalysts to produce methylamine electrocatalytically through the co-reduction of NO3− and CO2 and found that the MoCo-Pc-Pt-N5Por COFs, MoNi-Pc-Pt-N5Por COFs, and MoRu-Pc-Pt-N5Por COFs were the most effective electrocatalysts. Also, we found that the metallic TM atoms in the catalysts with the NO3− and CO2 molecules with the coexistence of charge depletion and charge accumulation behavior as the activation mechanism of NO3− and CO2. This work offers a theoretical foundation for experimental research and opens up new possibilities for the rational design of effective electrocatalytic NO3− and CO2 co-reduction catalysts for synthesizing methylamine.

A ruthenium single atom nanozyme-based antibiotic for the treatment of otitis media caused by Staphylococcus aureus.

Staphylococcus aureus (S. aureus) infection is a primary cause of otitis media (OM), the most common disease for which children are prescribed antibiotics. However, the abuse of antibiotics has led to a global increase in antimicrobial resistance (AMR). Nanozymes, as promising alternatives to traditional antibiotics, are being extensively utilized to combat AMR. Here, we synthesize a series of single-atom nanozymes (metal-C3N4 SANzymes) by loading four metals (Ag, Fe, Cu, Ru) with antibacterial properties onto a crystalline g-C3N4. These metal-C3N4 display a rob-like morphology and well-dispersed metal atoms. Among them, Ru-C3N4 demonstrates the optimal peroxidase-like activity (285.3 U mg-1), comparable to that of horseradish peroxidase (267.7 U mg-1). In vitro antibacterial assays reveal that Ru-C3N4 significantly inhibits S. aureus growth compared with other metal-C3N4 even at a low concentration (0.06mg mL-1). Notably, Ru-C3N4 acts as a narrow-spectrum nanoantibiotic with relative specificity against Gram-positive bacteria. Biofilms formed by S. aureus are easily degraded by Ru-C3N4 due to its high peroxidase-like activity. In vivo, Ru-C3N4 effectively eliminates S. aureus and relieves ear inflammation in OM mouse models. However, untreated OM mice eventually develop hearing impairment. Due to its low metal load, Ru-C3N4 does not exhibit significant toxicity to blood, liver, or kidney. In conclusion, this study presents a novel SANzyme-based antibiotic that can effectively eliminate S. aureus and treat S. aureus-induced OM.

Substituents' Effect on the Photophysics of Trinuclear Copper(I) and Silver(I) Pyrazolate-Phosphine Cages.

A series of structurally similar trinuclear macrocyclic copper(I) and silver(I) pyrazolate complexes bearing various short-bite diphosphine R2PCH(R')PR2 ligands are reported. Upon diphosphine coordination, the planar geometry of the initial complexes undergoes bending along the line between two metal atoms coordinated to the phosphorus moieties. The complexes based on dcpm ligands (R = cyclohexyl, R' = H, Ph) do not exhibit dynamic behavior in solution at room temperature on the 31P NMR time scale as it was previously observed for similar trinuclear copper complexes bearing the dppm (R = Ph, R' = H) scaffold. All copper(I) complexes exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. Importantly, the use of aliphatic substituents on the phosphorus atoms instead of aromatic ones leads to an almost double increase in the quantum efficiency (ΦPL) of photoluminescence by eliminating nonradiative decay from the 3LCPh states of the dppm aromatic rings. The higher donating ability of the substituents in the pyrazolate ligand (CF3 vs CH3) lowers the energy of the metal-centered excited state, allowing for a significant metal impact on the T1 state. Finally, the Ag(I) complex displays an emission efficiency of approximately 14%, being the highest among known trinuclear silver(I) pyrazolate homometallic derivatives.

Two-dimensional conjugated metal–organic frameworks grown on a MoS2 surface

Molybdenum disulfide (MoS2) features an atomically flat surface without dangling bonds. Molecular self-assembly on this surface provides an effective route to constructing heterostructure devices. In this work, we show the successful synthesis of M3(1,4,5,8,9,12-hexaazatriphenylene, HAT)2 (M = Ni, Co) conjugated metal–organic frameworks (c-MOFs) on a MoS2 surface. In the frameworks, HAT molecules constitute a honeycomb lattice while the metal atoms constitute a Kagome lattice. The random orientations of the frameworks with respect to the substrate and irregular domain shapes indicate that the frameworks interact weakly with the MoS2. The successful synthesis of 2D c-MOFs on inert substrates opens a door for the construction of advanced 2D van der Waals heterojunctions.

Customized Heteronuclear Dual Single-Atom and Cluster Assemblies via D-Band Orchestration for Oxygen Reduction Reaction.

Advanced oxygen reduction reaction (ORR) catalysts, integrating with well-dispersed single atom (SA) and atomic cluster (AC) sites, showcase potential in bolstering catalytic activity. However, the precise structural modulation and in-depth investigation of their catalytic mechanisms pose ongoing challenges. Herein, a proactive cluster lockdown strategy is introduced, relying on the confinement of trinuclear clusters with metal atom exchange in the covalent organic polymers, enabling the targeted synthesis of a series of multicomponent ensembles featuring FeCo (Fe or Co) dual-single-atom (DSA) and atomic cluster (AC) configurations (FeCo-DSA/AC) via thermal pyrolysis. The designed FeCo-DSA/AC surpasses Fe- and Co-derived counterparts by 18 mV and 49 mV in ORR half-wave potential, whilst exhibiting exemplary performance in Zn-air batteries. Comprehensive analysis and theoretical simulation elucidate the enhanced activity stems from adeptly orchestrating dz 2-dxz and O 2p orbital hybridization proximate to the Fermi level, fine-tuning the antibonding states to expedite OH* desorption and OOH* formation, thereby augmenting catalytic activity. This work elucidates the synergistic potentiation of active sites in hybrid electrocatalysts, pioneering innovative targeted design strategies for single-atom-cluster electrocatalysts.