Fixed-Point Atomic Regulation Engineered Low-Thickness Wideband Microwave Absorption.

Atomic doping is widely employed to fine-tune crystal structures, energy band structures, and the corresponding electrical properties. However, due to the difficulty in precisely regulating doping sites and concentrations, establishing a relationship between electricity properties and doping becomes a huge challenge. In this work, a modulation strategy on A-site cation dopant into spinel-phase metal sulfide Co9S8 lattice via Fe and Ni elements is developed to improve the microwave absorption (MA) properties. At the atomic scale, accurately controlling doped sites can introduce local lattice distortions and strain concentration. Tunned electron energy redistribution of the doped Co9S8 strengthens electron interactions, ultimately enhancing the high-frequency dielectric polarization (ɛ' from 10.5 to 12.5 at 12 GHz). For the Fe-doped Co9S8, the effective absorption bandwidth (EAB) at 1.7 mm increases by 5%, and the minimum reflection loss (RLmin) improves by 26% (EAB = 5.8 GHz, RLmin = -46 dB). The methodology of atomic-scale fixed-point doping presents a promising avenue for customizing the dielectric properties of nanomaterials, imparting invaluable insights for the design of cutting-edge high-performance microwave absorption materials.

Modulating d-Band Electronic Structures of Molybdenum Disulfide via p/n Doping to Boost Polysulfide Conversion in Lithium-Sulfur Batteries.

Polysulfide shuttle effect and sluggish sulfur reaction kinetics severely impede the cycling stability and sulfur utilization of lithium-sulfur (Li-S) batteries. Modulating d-band electronic structures of molybdenum disulfide electrocatalysts via p/n doping is promising to boost polysulfide conversion and suppress polysulfide migration in lithium-sulfur batteries. Herein, p-type V-doped MoS2 (V-MoS2 ) and n-type Mn-doped MoS2 (Mn-MoS2 ) catalysts are well-designed. Experimental results and theoretical analyses reveal that both of them significantly increase the binding energy of polysulfides on the catalysts' surface and accelerate the sluggish conversion kinetics of sulfur species. Particularly, the p-type V-MoS2 catalyst exhibits a more obvious bidirectional catalytic effect. Electronic structure analysis further demonstrates that the superior anchoring and electrocatalytic activities are originated from the upward shift of the d-band center and the optimized electronic structure induced by duplex metal coupling. As a result, the Li-S batteries with V-MoS2 modified separator exhibit a high initial capacity of 1607.2 mAh g-1 at 0.2 C and excellent rate and cycling performance. Moreover, even at a high sulfur loading of 6.84 mg cm-2 , a favorable initial areal capacity of 8.98 mAh cm-2 is achieved at 0.1 C. This work may bring widespread attention to atomic engineering in catalyst design for high-performance Li-S batteries.

Atomic Engineering of Clusterzyme for Relieving Acute Neuroinflammation through Lattice Expansion.

Natural enzymes are efficient and versatile biocatalysts but suffer in their environmental tolerance and catalytic stability. As artificial enzymes, nanozymes can improve the catalytic stability, but it is still a challenge to achieve high catalytic activity. Here, we employed atomic engineering to build the artificial enzyme named Au24Ag1 clusterzyme that hosts an ultrahigh catalytic activity as well as strong physiological stability via atom manipulation. The designed Au24Ag1 clusterzyme activates the Ag-S active site via lattice expansion in the oligomer atom layer, showing an antioxidant property 72 times higher than that of natural antioxidant Trolox. Enzyme-mimicked studies find that Au24Ag1 clusterzyme exhibits high catalase-like (CAT-like) and glutathione peroxidase-like (GPx-like) activity with a maximum reaction rate of 68.9 and 17.8 µM/min, respectively. Meanwhile, the unique catalytic landscape exhibits distinctive reactions against inflammation by inhibiting the cytokines at an early stage in the brain. Atomic engineering of clusterzymes provides a powerful and attractive platform with satisfactory atomic dispersion for tailoring biocatalysts freely at the atomic level.

Atomic Engineering of Single-Atom Nanozymes for Biomedical Applications.

Single-atom nanozymes (SAzymes) showcase not only uniformly dispersed active sites but also meticulously engineered coordination structures. These intricate architectures bestow upon them an exceptional catalytic prowess, thereby captivating numerous minds and heralding a new era of possibilities in the biomedical landscape. Tuning the microstructure of SAzymes on the atomic scale is a key factor in designing targeted SAzymes with desirable functions. This review first discusses and summarizes three strategies for designing SAzymes and their impact on reactivity in biocatalysis. The effects of choices of carrier, different synthesis methods, coordination modulation of first/second shell, and the type and number of metal active centers on the enzyme-like catalytic activity are unraveled. Next, a first attempt is made to summarize the biological applications of SAzymes in tumor therapy, biosensing, antimicrobial, anti-inflammatory, and other biological applications from different mechanisms. Finally, how SAzymes are designed and regulated for further realization of diverse biological applications is reviewed and prospected. It is envisaged that the comprehensive review presented within this exegesis will furnish novel perspectives and profound revelations regarding the biomedical applications of SAzymes.

Current Advances on the Single-Atom Nanozyme and Its Bioapplications.

Nanozymes, a class of nanomaterials mimicking the function of enzymes, have aroused much attention as the candidate in diverse fields with the arbitrarily tunable features owing to the diversity of crystalline nanostructures, composition, and surface configurations. However, the uncertainty of their active sites and the lower intrinsic deficiencies of nanomaterial-initiated catalysis compared with the natural enzymes promote the pursuing of alternatives by imitating the biological active centers. Single-atom nanozymes (SAzymes) maximize the atom utilization with the well-defined structure, providing an important bridge to investigate mechanism and the relationship between structure and catalytic activity. They have risen as the new burgeoning alternative to the natural enzyme from in vitro bioanalytical tool to in vivo therapy owing to the flexible atomic engineering structure. Here, focus is mainly on the three parts. First, a detailed overview of single-atom catalyst synthesis strategies including bottom-up and top-down approaches is given. Then, according to the structural feature of single-atom nanocatalysts, the influence factors such as central metal atom, coordination number, heteroatom doping, and the metal-support interaction are discussed and the representative biological applications (including antibacterial/antiviral performance, cancer therapy, and biosensing) are highlighted. In the end, the future perspective and challenge facing are demonstrated.

Pd Atomic Engineering of Nanoporous Ni/NiO for Efficient Nitrophenol Hydrogenation Reaction.

The catalytic hydrogenation of nitrophenols is widely utilized for both industrial synthesis and environmental protection, thus efficient and cost-effective catalysts are in urgent need. Still, the cost and scarcity of the materials still inhibit their application and the active sites are not well specified, especially in the complex catalysts. Herein, we developed an atomic Pd-doped nanoporous Ni/NiO (Pd1@np-Ni/NiO) catalyst via facial dealloying for efficient nitrophenol hydrogenation reaction under mild conditions. Pd1@np-Ni/NiO achieves an excellent specific activity (1301 min-1 mgPd-1, 35.2 times that of commercial Pd/C), nearly 100% selectivity, and continuous reproducibility. The catalytic performance is highly relevant to the Ni sites on the catalysts regarding the exposure sites and the intrinsic property. The metal/metal oxide interfacial structure could cooperatively accelerate the catalytic reaction kinetics. The atomic dopants could effectively modulate the electronic structure, facilitate the absorption of molecules, and reduce the energy barrier of catalytic hydrogenation reaction. Based on the efficient catalyst, the protype nitrophenol//NaBH4 battery is designed for efficient material conversion and power output, which is very attractive for green energy systems.

Metal-organic framework-derived magnetic carbon for efficient decontamination of organic pollutants via periodate activation: Surface atomic structure and mechanistic considerations.

Practical implementation of periodate-based advanced oxidation processes for environmental remediation largely relies on the development of cost-effective and high-performance activators. Surface atomic engineering toward these activators is desirable but it remains challenging to realize improved activation properties. Here, a surface atomic engineering strategy used to obtain a novel hybrid activator, namely cobalt-coordinated nitrogen-doped graphitic carbon nanosheet-enwrapped cobalt nanoparticles (denoted as Co@NC-rGO), from a sandwich-architectured metal-organic framework/graphene oxide composite is reported. This activator exhibits prominent periodate activation properties toward pollutant degradation, surpassing previously reported transition-metal-based activators. Importantly, the activator shows good stability, magnetic reusability, and the potential for application in a complex water matrix. Density functional theory modeling implies that the strong activation capability of Co@NC-rGO is related to its surface atomic structure for which the embedded cobalt nanoparticles with abundant interfacial Co-N coordinations display modified electronic configurations on the active centers and benefit periodate adsorption. Quenching experiments and electrochemical measurements showed that the system could oxidize organics through a dominant nonradical pathway. Additionally, a lower concentration of cobalt leaching was observed for the Co@NC-rGO/periodate system than for its Co@NC-rGO/persulfate counterpart. Our work provides a pathway toward engineering surface atomic structures in hybrid activators for efficient periodate activation.

Bifunctional Monolayer WSe2/Graphene Self-Stitching Heterojunction Microreactors for Efficient Overall Water Splitting in Neutral Medium.

Developing efficient bifunctional electrocatalysts in neutral media to avoid the deterioration of electrodes or catalysts under harsh environments has become the ultimate goal in electrochemical water splitting. This work demonstrates the fabrication of an on-chip bifunctional two-dimensional (2D) monolayer (ML) WSe2/graphene heterojunction microreactor for efficient overall water splitting in a neutral medium (pH = 7). Through the synergistic atomic growth of the metallic Cr dopant and graphene stitching contact on the 2D ML WSe2, the bifunctional WSe2/graphene heterojunction microreactor consisting of a full-cell configuration demonstrates excellent performance for overall water splitting in a neutral medium. Atomic doping of metallic Cr atoms onto the 2D ML WSe2 effectively facilitates the charge transfer at the solid-liquid interface. In addition, the direct growth of the self-stitching graphene contact with the 2D WSe2 catalyst largely reduces the contact resistance of the microreactor and further improves the overall water splitting efficiency. A significant reduction of the overpotential of nearly 1000 mV at 10 mA cm-2 at the Cr-doped WSe2/graphene heterojunction microreactor compared to the ML pristine WSe2 counterpart is achieved. The bifunctional WSe2/graphene self-stitching heterojunction microreactor is an ideal platform to investigate the fundamental mechanism of emerging bifunctional 2D catalysts for overall water splitting in a neutral medium.

Atomic-engineering Au-Ag nanoalloys for screening antimicrobial agents with low toxicity towards mammalian cells.

Silver nanoparticles (AgNPs) have shown potent antibacterial activity against numerous bacteria strains. However, their toxicity against mammalian cells is still a big challenge, limiting their in vivo applications. Here, we found that alloying Ag and Au in an atomic level to form Au-Ag nanoalloys (NAs) could effectively reduce the cytotoxicity of AgNPs, and the antimicrobial activity of NAs could be well maintained by tuning the composition of Ag. By means of a facile and robust laser-based technique, which involves the laser ablation of metal films toward water (LATW), we fabricated a series of Au-Ag NAs with different elemental compositions. Precise control over the compositions of Au and Ag was achieved via adjusting the thickness ratio of ablated Au/Ag films. Following the systematic examinations of these NAs on their antibacterial performance and the toxicity against the normal mammalian cells, we found that significant bactericidal effect with negligible cytotoxicity could be achieved with the NAs bearing 40 % of Au and 60 % Ag. Furthermore, Au-Ag NAs displayed a lower cytotoxicity than their corresponding monometallic NP mixtures due to the decreased Ag+ release from alloying structures of Au-Ag. This work showed the great potential of Au-Ag NAs in in vivo applications to fight against bacterial infections.

Exsolution of Embedded Nanoparticles in Defect Engineered Perovskite Layers.

Exsolution phenomena are highly debated as efficient synthesis routes for nanostructured composite electrode materials for the application in solid oxide cells (SOCs) and the development of next-generation electrochemical devices for energy conversion. Utilizing the instability of perovskite oxides, doped with electrocatalytically active elements, highly dispersed nanoparticles can be prepared at the perovskite surface under the influence of a reducing heat treatment. For the systematic study of the mechanistic processes governing metal exsolution, epitaxial SrTi0.9Nb0.05Ni0.05O3-δ thin films of well-defined stoichiometry are synthesized and employed as model systems to investigate the interplay of defect structures and exsolution behavior. Spontaneous phase separation and the formation of dopant-rich features in the as-synthesized thin film material is revealed by high-resolution transmission electron microscopy (HR-TEM) investigations. The resulting nanostructures are enriched by nickel and serve as preformed nuclei for the subsequent exsolution process under reducing conditions, which reflects a so far unconsidered process drastically affecting the understanding of nanoparticle exsolution phenomena. Using an approach of combined morphological, chemical, and structural analysis of the exsolution response, a limitation of the exsolution dynamics for nonstoichiometric thin films is found to be correlated to a distortion of the perovskite host lattice. Consequently, the incorporation of defect structures results in a reduced particle density at the perovskite surface, presumably by trapping of nanoparticles in the oxide bulk.

Self-Activated Catalytic Sites on Nanoporous Dilute Alloy for High-Efficiency Electrochemical Hydrogen Evolution.

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction (HER) in wide pH environments are critical to reduce energy losses in water electrolyzers. Here, by using a self-activation strategy, we construct an atomic nickel (Ni) decorated nanoporous iridium (Ir) catalyst, which can create the reaction-favorable chemical environment and maximize the electrochemical active surface area (ECSA), enabling efficient HER over a wide pH range. By using operando X-ray absorption spectroscopy and theoretical calculations, the atomic Ni sites are identified as the synergistic sites, which not only accelerate the water dissociation under operation conditions but also activate the surface Ir sites thus leading to the efficient H2 generation. This work highlights the significance of atomic-level decorating strategy which can optimize the activity of surface Ir atoms with negligible sacrifice of the ECSA.