Enhancing the activity of Pd ensembles on graphene by manipulating coordination environment.

Atomic dispersion of metal catalysts on a substrate accounts for the increased atomic efficiency of single-atom catalysts (SACs) in various catalytic schemes compared to the nanoparticle counterparts. However, lacking neighboring metal sites has been shown to deteriorate the catalytic performance of SACs in a few industrially important reactions, such as dehalogenation, CO oxidation, and hydrogenation. Metal ensemble catalysts (Mn), an extended concept to SACs, have emerged as a promising alternative to overcome such limitation. Inspired by the fact that the performance of fully isolated SACs can be enhanced by tailoring their coordination environment (CE), we here evaluate whether the CE of Mn can also be manipulated in order to enhance their catalytic activity. We synthesized a set of Pd ensembles (Pdn) on doped graphene supports (Pdn/X-graphene where X = O, S, B, and N). We found that introducing S and N onto oxidized graphene modifies the first shell of Pdn converting Pd-O to Pd-S and Pd-N, respectively. We further found that the B dopant significantly affected the electronic structure of Pdn by serving as an electron donor in the second shell. We examined the performance of Pdn/X-graphene toward selective reductive catalysis, such as bromate reduction, brominated organic hydrogenation, and aqueous-phase CO2 reduction. We observed that Pdn/N-graphene exhibited superior performance by lowering the activation energy of the rate-limiting step, i.e., H2 dissociation into atomic hydrogen. The results collectively suggest controlling the CE of SACs in an ensemble configuration is a viable strategy to optimize and enhance their catalytic performance.

Slow-release synthesis of Cu single-atom catalysts with the optimized geometric structure and density of state distribution for Fenton-like catalysis.

Single-atom Fenton-like catalysis has attracted significant attention, yet the quest for controllable synthesis of single-atom catalysts (SACs) with modulation of electron configuration is driven by the current disadvantages of poor activity, low selectivity, narrow pH range, and ambiguous structure-performance relationship. Herein, we devised an innovative strategy, the slow-release synthesis, to fabricate superior Cu SACs by facilitating the dynamic equilibrium between metal precursor supply and anchoring site formation. In this strategy, the dynamics of anchoring site formation, metal precursor release, and their binding reaction kinetics were regulated. Bolstered by harmoniously aligned dynamics, the selective and specific monatomic binding reactions were ensured to refine controllable SACs synthesis with well-defined structure-reactivity relationship. A copious quantity of monatomic dispersed metal became deposited on the C3N4/montmorillonite (MMT) interface and surface with accessible exposure due to the convenient mass transfer within ordered MMT. The slow-release effect facilitated the generation of targeted high-quality sites by equilibrating the supply and demand of the metal precursor and anchoring site and improved the utilization ratio of metal precursors. An excellent Fenton-like reactivity for contaminant degradation was achieved by the Cu1/C3N4/MMT with diminished toxic Cu liberation. Also, the selective ·OH-mediated reaction mechanism was elucidated. Our findings provide a strategy for regulating the intractable anchoring events and optimizing the microenvironment of the monatomic metal center to synthesize superior SACs.

A green edge-hosted zinc single-site heterogeneous catalyst for superior Fenton-like activity.

Developing green heterogeneous catalysts with excellent Fenton-like activity is critical for water remediation technologies. However, current catalysts often rely on toxic transitional metals, and their catalytic performance is far from satisfactory as alternatives of homogeneous Fenton-like catalysts. In this study, a green catalyst based on Zn single-atom was prepared in an ammonium atmosphere using ZIF-8 as a precursor. Multiple characterization analyses provided evidence that abundant intrinsic defects due to the edge sites were created, leading to the formation of a thermally stable edge-hosted Zn-N4 single-atom catalyst (ZnN4-Edge). Density functional theory calculations revealed that the edge sites equipped the single-atom Zn with a super catalytic performance, which not only promoted decomposition of peroxide molecule (HSO5-) but also greatly lowered the activation barrier for •OH generation. Consequently, the as-prepared ZnN4-Edge exhibited extremely high Fenton-like performance in oxidation and mineralization of phenol as a representative organic contaminant in a wide range of pH, realizing its quick detoxification. The atom-utilization efficiency of the ZnN4-Edge was ~104 higher than an equivalent amount of the control sample without edge sites (ZnN4), and the turnover frequency was ~103 times of the typical benchmark of homogeneous catalyst (Co2+). This study opens up a revolutionary way to rationally design and optimize heterogeneous catalysts to homogeneous catalytic performance for Fenton-like application.

Atomic coordination environment engineering of bimetallic alloy nanostructures for efficient ammonia electrosynthesis from nitrate.

Electrochemical nitrate reduction reaction (NO3RR) to ammonia has been regarded as a promising strategy to balance the global nitrogen cycle. However, it still suffers from poor Faradaic efficiency (FE) and limited yield rate for ammonia production on heterogeneous electrocatalysts, especially in neutral solutions. Herein, we report one-pot synthesis of ultrathin nanosheet-assembled RuFe nanoflowers with low-coordinated Ru sites to enhance NO3RR performances in neutral electrolyte. Significantly, RuFe nanoflowers exhibit outstanding ammonia FE of 92.9% and yield rate of 38.68 mg h-1 mgcat-1 (64.47 mg h-1 mgRu-1) at -0.30 and -0.65 V (vs. reversible hydrogen electrode), respectively. Experimental studies and theoretical calculations reveal that RuFe nanoflowers with low-coordinated Ru sites are highly electroactive with an increased d-band center to guarantee efficient electron transfer, leading to low energy barriers of nitrate reduction. The demonstration of rechargeable zinc-nitrate batteries with large-specific capacity using RuFe nanoflowers indicates their great potential in next-generation electrochemical energy systems.

Oxygen doping of cobalt-single-atom coordination enhances peroxymonosulfate activation and high-valent cobalt-oxo species formation.

The high-valent cobalt-oxo species (Co(IV)=O) is being increasingly investigated for water purification because of its high redox potential, long half-life, and antiinterference properties. However, generation of Co(IV)=O is inefficient and unsustainable. Here, a cobalt-single-atom catalyst with N/O dual coordination was synthesized by O-doping engineering. The O-doped catalyst (Co-OCN) greatly activated peroxymonosulfate (PMS) and achieved a pollutant degradation kinetic constant of 73.12 min-1 g-2, which was 4.9 times higher than that of Co-CN (catalyst without O-doping) and higher than those of most reported single-atom catalytic PMS systems. Co-OCN/PMS realized Co(IV)=O dominant oxidation of pollutants by increasing the steady-state concentration of Co(IV)=O (1.03 × 10-10 M) by 5.9 times compared with Co-CN/PMS. A competitive kinetics calculation showed that the oxidation contribution of Co(IV)=O to micropollutant degradation was 97.5% during the Co-OCN/PMS process. Density functional theory calculations showed that O-doping influenced the charge density (increased the Bader charge transfer from 0.68 to 0.85 e), optimized the electron distribution of the Co center (increased the d-band center from -1.14 to -1.06 eV), enhanced the PMS adsorption energy from -2.46 to -3.03 eV, and lowered the energy barrier for generation of the key reaction intermediate (*O*H2O) during Co(IV)=O formation from 1.12 to 0.98 eV. The Co-OCN catalyst was fabricated on carbon felt for a flow-through device, which achieved continuous and efficient removal of micropollutants (degradation efficiency of >85% after 36 h operation). This study provides a new protocol for PMS activation and pollutant elimination through single-atom catalyst heteroatom-doping and high-valent metal-oxo formation during water purification.

Regulating Second Coordination Shell of Ce Atom Site and Reshaping of Carrier Enable Single-Atom Nanozyme to Efficiently Express Oxidase-like Activity.

Single-atom nanozymes (SANs) are considered to be ideal substitutes for natural enzymes due to their high atom utilization. This work reported a strategy to manipulate the second coordination shell of the Ce atom and reshape the carbon carrier to improve the oxidase-like activity of SANs. Internally, S atoms were symmetrically embedded into the second coordination layer to form a Ce-N4S2-C structure, which reduced the energy barrier for O2 reduction, promoted the electron transfer from the Ce atom to O atoms, and enhanced the interaction between the d orbital of the Ce atom and p orbital of O atoms. Externally, in situ polymerization of mussel-inspired polydopamine on the precursor helps capture metal sources and protects the 3D structure of the carrier during pyrolysis. On the other hand, polyethylene glycol (PEG) modulated the interface of the material to enhance water dispersion and mass transfer efficiency. As a proof of concept, the constructed PEG@P@Ce-N/S-C was applied to the multimodal assay of butyrylcholinesterase activity.

Coordination Environment Engineering to Regulate the Adsorption Strength of Intermediates in Single Atom Catalysts for High-performance CO2 Reaction Reduction.

The modulation of the coordination environment of single atom catalysts (SACs) plays a vital role in promoting CO2 reduction reaction (CO2RR). Herein, N or B doped Fe-embedded graphyne (Fe-GY), Fe-nXGYm (n = 1, 2, 3; X = N, B; m = 1, 2, 3), are employed as probes to reveal the effect of the coordination environment engineering on CO2RR performance via heteroatom doping in SACs. The results show that the doping position and number of N or B in Fe-GY significantly affects catalyst activity and CO2RR product selectivity. In comparison, Fe-1NGY exhibits high-performance CO2RR to CH4 with a low limiting potential of -0.17 V, and Fe-2NGY3 is demonstrated as an excellent CO2RR electrocatalyst for producing HCOOH with a low limiting potential of -0.16 V. With applied potential, Fe-GY, Fe-1NGY, and Fe-2NGY3 exhibit significant advantages in CO2RR to CH4 while hydrogen evolution reaction is inhibited. The intrinsic essence analysis illustrates that heteroatom doping modulates the electronic structure of active sites and regulates the adsorption strength of the intermediates, thereby rendering a favorable coordination environment for CO2RR. This work highlights Fe-nXGYm as outstanding SACs for CO2RR, and provides an in-depth insight into the intrinsic essence of the promotion effect from heteroatom doping.

Accelerating Sulfur Redox Chemistry by Atomically Dispersed Zn-N4 Sites Coupled with Pyridine-N Defects on Porous Carbon Sheets.

Single-atom catalysts (SACs) with specific N-coordinated configurations immobilized on the carbon substrates have recently been verified to effectively alleviate the shuttle effect of lithium polysulfides (LiPSs) in lithium-sulfur (Li─S) batteries. Herein, a versatile molten salt (KCl/ZnCl2 )-mediated pyrolysis strategy is demonstrated to fabricate Zn SACs composed of well-defined Zn-N4 sites embedded into porous carbon sheets with rich pyridine-N defects (Zn─N/CS). The electrochemical kinetic analysis and theoretical calculations reveal the critical roles of Zn-N4 active sites and surrounding pyridine-N defects in enhancing adsorption toward LiPS intermediates and catalyzing their liquid-solid conversion. It is confirmed by reducing the overpotential of the rate-determining step of Li2 S2 to Li2 S and the energy barrier for Li2 S decomposition, thus the Zn─N/CS guarantees fast redox kinetics between LiPSs and Li2 S products. As a proof of concept demonstration, the assembled Li─S batteries with the Zn─N/CS-based sulfur cathode deliver a high specific capacity of 1132 mAh g-1 at 0.1 C and remarkable capacity retention of 72.2% over 800 cycles at 2 C. Furthermore, a considerable areal capacity of 6.14 mAh cm-2 at 0.2 C can still be released with a high sulfur loading of 7.0 mg cm-2 , highlighting the practical applications of the as-obtained Zn─N/CS cathode in Li─S batteries.

Modulating the Coordination Environment of Carbon-Dot-Supported Fe Single-Atom Nanozymes for Enhanced Tumor Therapy.

Herein, carbon dot (CD)-supported Fe single-atom nanozymes with high content of pyrrolic N and ultrasmall size (ph-CDs-Fe SAzyme) are fabricated by a phenanthroline-mediated ligand-assisted strategy. Compared with phenanthroline-free nanozymes (CDs-Fe SAzyme), ph-CDs-Fe SAzyme exhibit higher peroxidase (POD)-like activity due to their structure similar to that of ferriporphyrin in natural POD. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analyses show that metal Fe is dispersed in ph-CDs-Fe SAzyme as single atoms. Steady-state kinetic studies show that the maximum velocity (Vmax ) and turnover number (kcat ) of H2 O2  homolytic cleavage catalyzed by ph-CDs-Fe SAzyme are 3.0 and 6.2 more than those of the reaction catalyzed by CDs-Fe SAzyme. Density functional theory (DFT) calculations show that the energy barrier of the reaction catalyzed by ph-CDs-Fe SAzyme is lower than that catalyzed by CDs-Fe SAzyme. Antitumor efficacy experiments show that ph-CDs-Fe SAzyme can efficiently inhibit the growth of tumor cells both in vitro and in vivo by synergistic chemodynamic and photothermal effects. Here a new paradigm is provided for the development of efficient antitumor therapeutic approaches based on SAzyme with POD-like activity.

Copper Single-Atom Catalysts-A Rising Star for Energy Conversion and Environmental Purification: Synthesis, Modification, and Advanced Applications.

Future renewable energy supply and green, sustainable environmental development rely on various types of catalytic reactions. Copper single-atom catalysts (Cu SACs) are attractive due to their distinctive electronic structure (3d orbitals are not filled with valence electrons), high atomic utilization, and excellent catalytic performance and selectivity. Despite numerous optimization studies are conducted on Cu SACs in terms of energy conversion and environmental purification, the coupling among Cu atoms-support interactions, active sites, and catalytic performance remains unclear, and a systematic review of Cu SACs is lacking. To this end, this work summarizes the recent advances of Cu SACs. The synthesis strategies of Cu SACs, metal-support interactions between Cu single atoms and different supports, modification methods including modification for carriers, coordination environment regulating, site distance effect utilizing, and dual metal active center catalysts constructing, as well as their applications in energy conversion and environmental purification are emphatically introduced. Finally, the opportunities and challenges for the future Cu SACs development are discussed. This review aims to provide insight into Cu SACs and a reference for their optimal design and wide application.

Precise Atomic Structure Regulation of Single-Atom Platinum Catalysts toward Highly Efficient Hydrogen Evolution Reaction.

Noble metal single-atom-catalysts (SACs) have demonstrated significant potential to improve atom utilization efficiency and catalytic activity for hydrogen evolution reaction (HER). However, challenges still remain in rationally modulating active sites and catalytic activities of SACs, which often results in sluggish kinetics and poor stability, especially in neutral/alkaline media. Herein, precise construction of Pt single atoms anchored on edge of 2D layered Ni(OH)2 (Pt-Ni(OH)2-E) is achieved utilizing in situ electrodeposition. Compared to the single-atom Pt catalysts anchored on the basal plane of Ni(OH)2 (Pt-Ni(OH)2-BP), the Pt-Ni(OH)2-E possesses superior electron affinity and high intrinsic catalytic activity, which favors the strong adsorption and rapid dissociation toward water molecules. As a result, the Pt-Ni(OH)2-E catalyst requires low overpotentials of 21 and 34 mV at 10 mA cm-2 in alkaline and neutral conditions, respectively. Specifically, it shows the high mass activity of 23.6 A mg-1 for Pt at the overpotential of 100 mV, outperforming the reported catalysts and commercial Pt/C. This work provides new insights into the rational design of active sites for preparing high-performance SACs.

Dual-Ligand Strategy to Construct Metal Organic Gel Catalyst with the Optimized Electronic Structure for High-Efficiency Overall Water Splitting and Flexible Metal-Air Battery.

Non-noble metal catalysts are known for their efficient catalytic performance for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Metal organic gels (MOGs) can be considered as a promising electrocatalyst owing to the diverse physicochemical properties but usually suffer from its poor electrical conductivity and catalytic stability. Here, a FeCo-MOG is constructed with considerable trifunctional activity. The optimal P-CoFe-H3 prepared by using phytic acid (PA) and 2,4,6-Tris[(p-carboxyphenyl)amino]-1,3,5-triazine benzoic acid (H3TATAB) as dual ligands), exhibits outstanding ORR, OER, and HER activities as well as stability, exceeding most of state-of-the-art catalysts. As expected, the flexible Zn-air battery applied with P-CoFe-H3 as air cathode displays considerable power density, discharge voltage plateau, and cycling stability. Impressively, it is also capable of driving the overall water-splitting device by applying the P-CoFe-H3 as anode and cathode. Furthermore, theoretical calculations reveal that dual ligands can optimize the coordination environment and charge density of active sites, thereby reducing the absorption energy of intermediate species and boosting the catalytic performance. This work endows the dual-ligands coordination strategy with great potentiality for MOGs-based electrocatalysts in energy conversion devices.

Facilitation of Fenton-Like Reaction of Copper-Nitrogen-Doped Carbon-Based Nanocatalysts by Enhancing Hydroxyl Adsorption on Single-Atom Cu-NxC4- x Sites.

Copper-nitrogen-doped carbon-based nanocatalysts (Cu-NCs), containing atomically dispersed Cu-NxC4- x sites, are efficient in boosting the Fenton-like reaction. However, the mechanisms of the Fenton-like reaction, including the pH effect on the products and the effect of the coordination environment on catalytic activity, remain controversial, restricting the development of Cu-NCs. Cu-NCs are experimentally synthesized with Cu-N4 sites and prove that the Fenton-like reaction generates mainly hydroxyl radicals (·OH) in the acidic but ·OH and superoxide radicals (·O2 -) in the neutral. The density functional theory (DFT) calculations reveal that the catalytic activity of Cu-NCs in the Fenton-like reaction is associated with the adsorption strength of ·OH at the Cu site. Further investigation of the effect of the coordination environment of Cu-NCs indicates that the Cu-N2C2 site, which can enhance the ·OH adsorption strength, is an ideal catalyst site for the Fenton-like reaction. These results open the way to facilitating the catalytic activity of Cu-NCs in the Fenton-like reaction.

Boosting Efficient Alkaline Hydrogen Evolution Reaction of CoFe-Layered Double Hydroxides Nanosheets via Co-Coordination Mechanism of W-Doping and Oxygen Defect Engineering.

While surface defects and heteroatom doping exhibit promising potential in augmenting the electrocatalytic hydrogen evolution reaction (HER), their performance remains unable to rival that of the costly Pt-based catalysts. Yet, the concurrent modification of catalysts by integrating both approaches stands as a promising strategy to effectively address the aforementioned limitation. In this work, tungsten dopants are introduced into self-supported CoFe-layered double hydroxides (LDH) on nickel foam using a hydrothermal method, and oxygen vacancies (Ov) are further introduced through calcination. The analysis results demonstrated that tungsten doping reduces the Ov formation energy of CoFeW-LDH. The Ov acted as oxophilic sites, facilitating water adsorption and dissociation, and reducing the barrier for cleaving HO─H bonds from 0.64 to 0.14 eV. Additionally, Ov regulated the electronic structure of CoFeW-LDH to endow optimized hydrogen binding ability on tungsten atoms, thereby accelerating alkaline Volmer and Heyrovsky reaction kinetics. Specifically, the abundance of Ov induced a transition of tungsten from a six-coordinated to highly active four-coordinated structure, which becomes the active site for HER. Consequently, an ultra-low overpotential of 41 mV at 10 mA cm-2, and a low Tafel slope of 35 mV dec-1 are achieved. These findings offer crucial insights for the design of efficient HER electrocatalysts.

Curved Structure Regulated Single Metal Sites for Advanced Electrocatalytic Reactions.

Curved surface with defined local electronic structures and regulated surface microenvironments is significant for advanced catalytic engineering. Since single-atom catalysts are highly efficient and active, they have attracted much attention in recent years. The curvature carrier has a significant effect on the electronic structure regulation of single-atom sites, which effectively promote the catalytic efficiency. Here, the effect of the curvature structure with exposed metal atoms for catalysis is comprehensively summarized. First, the substrates with curvature features are reviewed. Second, the applications of single-atom catalysts containing curvature in a variety of different electrocatalytic reactions are discussed in depth. The impact of curvature effects in catalytic reactions is further analyzed. Finally, prospects and suggestions for their application and future development are presented. This review paves the way for the construction of high curvature-containing surface carriers, which is of great significance for single-atom catalysts development.

Modulating 3d Charge State via Halogen Ions in Neighboring Molecules of Metal-Organic Frameworks for Improving Water Oxidation.

Modulating the coordination environment of the metal active center is an effective method to boost the catalytic performances of metal-organic frameworks (MOFs) for oxygen evolution reaction (OER). However, little attention has been paid to the halogen effects on the ligands engineering. Herein, a series of MOFs X─FeNi-MOFs (X = Br, Cl, and F) is constructed with different coordination microenvironments to optimize OER activity. Theoretical calculations reveal that with the increase in electronegativity of halogen ions in terephthalic acid molecular (TPA), the Bader charge of Ni atoms gets larger and the Ni-3d band center and O-2p bands move closer to the Fermi level. This indicates that an increase in ligand negativity of halogen ions in TPA can promote the adsorption ability of catalytic sites to oxygen-containing intermediates and reduce the activation barrier for OER. Experimental also demonstrates that F─FeNi-MOFs exhibit the highest catalytic activity with an ultralow overpotential of 218 mV at 10 mA cm-2, outperforming most otate-of-the-art Fe/Co/Ni-based MOFs catalysts, and the enhanced mass activity by seven times compared with that for the sample before ligands engineering. This work opens a new avenue for the realization of the modulation of NiFe─O bonding by halogen ion in TPA and improves the OER performance of MOFs.

Single-Pd-Site Catalyst Induced by Different Dimensional Nitrogen of N-Doping Carbon for Efficient Hydroaminocarbonylation of Alkynes.

The unsaturated amides are traditionally synthesized by acylation of carboxylic acids or hydration of nitrile compounds but are rarely investigated by hydroaminocarbonylation of alkynes using heterogeneous single-metal-site catalysts (HSMSCs). Herein, single-Pd-site catalysts supported on N-doping carbon (NC) with different nitrogen dimensions inherited from corresponding metal-organic-framework precursors are successfully synthesized. 2D NC-supported single-Pd-site (Pd1/NC-2D) exhibited the best performance with near 100% selectivity and 76% yield of acrylamide for acetylene hydroaminocarbonylation with better stability, superior to those of Pd1/NC-3D, single-metal-site/nanoparticle coexisting catalyst, and nanoparticle catalyst. The coordination environment and molecular evolution of the single-Pd-site during the process of acetylene hydroaminocarbonylation on Pd1/NC-2D are detailly illuminated by various characterizations and density functional theoretical calculations (DFT). DFT also showed the energy barrier of rate-determining step on Pd1/NC-2D is lower than that of Pd1/NC-3D. Furthermore, Pd1/NC-2D catalyst illustrated the general applicability of the hydroaminocarbonylation for various alkynes.

Coordination Engineering of Heteronuclear Fe-Mo Dual-Atom Catalyst for Promoted Electrocatalytic Nitrogen Fixation: A DFT Study.

Developing efficient nanostructured electrocatalysts for N2 reduction to NH3 under mild conditions remains a major challenge. The Fe-Mo cofactor serves as the archetypal active site in nitrogenase. Inspired by nitrogenase, we designed a series of heteronuclear dual-atom catalysts (DACs) labeled as FeMoN6-a Xa (a=1, 2, 3; X=B, C, O, S) anchored on the pore of g-C3 N4 to probe the impact of coordination on FeMo-catalyzed nitrogen fixation. The stability, reaction paths, activity, and selectivity of 12 different FeMoN6-a Xa DACs have been systematically studied using density functional theory. Of these, four DACs (FeMoN5 B1 , FeMoN5 O1 , FeMoN4 O2 , and FeMoN3 C3 ) displayed promising nitrogen reduction reaction (NRR) performance. Notably, FeMoN5 O1 stands out with an ultralow limiting potential of -0.11 V and high selectivity. Analysis of the density of states and charge/spin changes shows FeMoN5 O1 's high activity arises from optimal N2 binding on Fe initially and synergy of the FeMo dimer enabling protonation in NRR. This work contributes to the advancement of rational design for efficient NRR catalysts by regulating atomic coordination environments.

Regulating the N Coordination Environment of Co Single-Atom Nanozymes for Highly Efficient Oxidase Mimics.

Single-atom catalysts with well-defined atomic structures and precisely regulated coordination environments have been recognized as potential substitutes for natural metalloenzymes. Inspired by the metal coordination structure of natural enzymes, we show here that the oxidase-like activity of single-atom Co catalysts greatly depends on their local N coordination around the Co catalytic sites. We synthesized a series of Co single-atom catalysts with different nitrogen coordination numbers (Co-Nx(C), x = 2, 3, and 4) and demonstrated that the oxidase-like activity of single-atom Co catalysts could be effectively tailored by fine-tuning the N coordination. Among the studied single-atom Co catalysts, the Co-N3(C) with three-coordinate N atoms shows the optimum oxygen adsorption structure and robust reactive oxygen species (ROS) generation, thus presenting the preferable oxidase-like catalytic activity. This work facilitates the future development of rational nanozyme designs for targeting reactions at the atomic level.

Grain-Boundary-Rich RuO2 Porous Nanosheet for Efficient and Stable Acidic Water Oxidation.

RuO2 has been considered as the most likely acidic oxygen evolution reaction (OER) catalyst to replace IrO2, but its performance, especially long-term stability under harsh acidic conditions, is still unacceptable. Here, we propose a grain boundary (GB) engineering strategy by fabricating the ultrathin porous RuO2 nanosheet with abundant of grain boundaries (GB-RuO2) as an efficient acid OER catalyst. The involvement of GB induces significant tensile stress and creates an unsaturated coordination environment, effectively optimizing the adsorption of intermediates and stabilizing active site structure during OER process. Notably, the GB-RuO2 not only exhibits a low overpotential (η10=187 mV) with an ultra-low Tafel slope (34.5 mV dec-1), but also steadily operates for over 550 h in 0.1 M HClO4. Quasi in situ/operando methods confirm that the improved stability is attributed to GB preventing Ru dissolution and greatly inhibiting the lattice oxygen oxidation mechanism (LOM). A proton exchange membrane water electrolysis (PEMWE) using the GB-RuO2 catalyst operates a low voltage of 1.669 V at 2 A cm-2 and operates stably for 100 h at 100 mA cm-2.