Single Ag Research Articles

Laser-Induced Self-Limiting Welding of Ag Nanowires with High Mechanical and Electrical Performance.

The high-efficiency and high-precision welding technology of Ag nanowires is of great engineering significance for the integration of new-generation micro- and nanodevices, and the mechanical behavior of its interconnect joints is also essential for their reliable application, especially for some flexible device. In this paper, based on the nano-focusing and localized plasma enhancement properties of Ag nanowires under laser irradiation, Ag nanowire self-limiting joints with mechanical and electrical properties comparable to those of the base material are obtained. At the same time, the local plasma enhancement characteristics of Ag nanowire joints are scanned and analyzed with nanoscale resolution by using cathodoluminescence technology, and the local multi-physical field coupling regulation mechanism of Ag nanowire joints induced by different laser parameters is systematically investigated by combining theoretical simulations. Meanwhile, based on the in situ laser welding and nanomechanical tensile experiments, the mechanical properties of single Ag nanowires and their welded joints are systematically analyzed, and the characteristics of the interfacial atomic behaviors and the evolution process during the welding and tensile processes are investigated.

Efficient nitrite-to-ammonia electroreduction on single Ag sites

Electroreduction of nitrite to ammonia (NO2RR) provides an innovative route for simultaneously achieving waste NO2– removal and valuable NH3 production. Herein, single-atom Ag on hexagonal BN nanosheets (Ag1@h-BN) is developed as an efficient catalyst for the NO2RR. Strikingly, Ag1@h-BN assembled in a flow cell shows the highest NH3-Faradaic efficiency of 92.04 % with the corresponding NH3 yield rate of 1523.6 μmol h−1 cm−2 at a high current density of 266.2 mA cm−2. Theoretical calculations and electrochemical spectroscopic measurements unveil the creation of Ag1-N3 site to selectively activate NO2– and boost the hydrogenation energetics of NO2–-to-NH3 pathway, consequently resulting in the substantially expedited selectivity and activity of Ag1@h-BN for the NO2RR.

Insight into the unique role of silver single-atom in atomic-thickness ZnIn2S4/g-C3N4 Van der Waals heterojunction for photocatalytic hydrogen evolution

The construction of ultra-close 2D atomic-thickness Van der Waals heterojunctions with high-speed charge transfer still faces challenges. Here, we synthesized single-layer ZnIn2S4 and g-C3N4, and introduced silver single atoms to regulate Van der Waals heterojunctions at the atomic level to optimize charge transfer and catalytic activity. At the atomic scale, the impact of detailed structural differences between the two characteristic surfaces of ZnIn2S4 ([Zn-S4] and [In-S4]) on catalytic performance has been first proposed. Experiments combined with the DFT study demonstrate that single atom Ag not only acts as a charge transfer bridge but also regulates the energy band and intrinsic catalytic activity. Benefiting from the enhanced electron delocalization, the synthesized catalyst ZIS/Ag@CN exhibits excellent photocatalytic performance, with a hydrogen production rate of 5.50 mmol·g−1·h−1, which is much higher than the reported Ag-based single-atom catalysts so far. This work provides a new understanding of atomic-level heterojunction interface regulation and modification.

Preparation of GaN Nanocrystals with Single Ag Cores

Preparation of GaN Nanocrystals with Single Ag Cores

Facile fabrication of Au-Ag alloy nanoparticles/Ag nanowires SERS substrates with bimetallic synergistic effect for ultra-sensitive detection of crystal violet and alkali blue 6B

The bimetallic nanostructure of Au and Ag can integrate two distinct properties into a novel substrate compared to single metal nanostructures. This work presents a rapid and sensitive surface-enhanced Raman scattering (SERS) substrate for detecting illegal food additives and dyes of crystal violet (CV) and alkali blue 6B (AB 6B). Au-Ag alloy nanoparticles/Ag nanowires (Au-Ag ANPs/Ag NWs) were prepared by solid-state ionics method and vacuum thermal evaporation method at 5μA direct current electric field (DCEF), the molar ratio of Au to Ag was 1:18.34. Many 40 nm-140 nm nanoparticles regularly existed on the surface of Ag NWs with the diameters from 80 nm to 150 nm. The fractal dimension of Au-Ag ANPs/Ag NWs is 1.69 due to macroscopic dendritic structures. Compared with single Ag NWs, the prepared Au-Ag ANPs/Ag NWs substrates show superior SERS performance because of higher surface roughness, the SERS active of Ag NWs and bimetallic synergistic effect caused by Au-Ag ANPs, so the limit of detections (LOD) of Au-Ag ANPs/Ag NWs SERS substrates toward detection of CV and AB 6B were as low as 10-16mol/L and 10-9mol/L, respectively. These results indicate that Au-Ag ANPs/Ag NWs substrates can be used for rapid and sensitive detection of CV and AB 6B and have great development potential for detection of illegal food additives and hazardous substances in the fields of environmental monitoring and food safety.

Anisotropic growth of Au-Ag heteronanostructures through plasmon-induced reduction.

Plasmonic heteronanostructures are promising building blocks for photofunctional materials and devices including photocatalysts, optical materials, and optoelectronic devices. In the present work, we fabricated Au-Ag bimetallic heteronanostructures based on site-selective and anisotropic Ag deposition and growth on Au nanocubes. Plasmonic Au nanocubes were adsorbed onto a glass plate, and the distal mode or proximal-distal mode of the nanocubes was selectively excited in the presence of Ag+ and citrate ions. Polycrystalline Ag was deposited around the top of the Au nanocubes by the distal mode excitation, and single crystalline Ag was grown laterally from the Au nanocubes by the proximal-distal mode excitation. The present method would be applied to the fabrication of various plasmonic nanostructures composed of two or more heterodomains.

C@Ag core-shell structure as lubricating additives towards high efficient lubrication

Efficient cooperative lubrication can be achieved via the introduction of core-shell structure lubricant additives with hard core and soft shell, for obtaining the expected anti-wear performance from the structural changes in the friction process. In this study, C@Ag microspheres with a core-shell structure were prepared by the redox method with carbon spheres as the core and Ag nanoparticles as the shell. Their tribological behaviors as base oil (G1830) additive with different concentrations were investigated in detail. Compared with base oil, the addition of C@Ag particles at 0.5 wt% can reduce the coefficient of friction (COF) and wear volume (Wv) up to 15.5% and 88%, respectively. More importantly, C@Ag particles provide superior lubrication performance to single additive (like carbon sphere (CS) and Ag nanoparticle). C@Ag core-shell particles contribute to the formation of tribo-film by melt bonding of flexible Ag and carbon sphere (CS) toward excellent self-repair performance and high-efficiency lubrication. Hence, core-shell structural nanoparticles with hard-core and soft-shell hold bright future for high-performance lubrication application.

Silver Single Atoms Combined with Clusters on Carbon Nanotubes Mediates Exclusive Electrochemical CO2‐to‐CO Conversion

AbstractThe electrochemical reduction of CO2 (eCO2RR) that exclusively produces one product at industrial current density is crucial for the substantial storage of renewable energy. Modulating the electronic structure of atomically dispersed catalysts can effectively regulate the adsorption of rate‐determining‐step intermediates to achieve the desired products. Here, the study constructs a hybrid catalyst consisting of single Ag atoms and Ag atomic clusters supported on nitrogen‐doped multi‐walled carbon nanotubes that can effectively regulate the important intermediate structure of *COOH. The X‐ray photoelectron and X‐ray absorption near‐edge spectroscopies demonstrate that turning Ag single atoms into Ag clusters can weaken the electron transfer between Ag–N and present a relatively rich electron state. Thus, the rate‐determining step of *COOH massive formation is significantly accelerated, as proven by in situ synchrotron infrared spectroscopy and density functional theory calculations. Using this strategy, a CO Faradaic efficiency outperforming 99% from −0.3 to −0.8 V (vs reversible hydrogen electrode) with current densities above 200 mA cm−2 and a half‐cell energetic efficiency of 86% is achieved. This work highlights a promising approach to advancing synergistic catalysts for achieving more controllable and efficient eCO2RR.

Effects of Raman Labeling Compounds on the Stability and Surface-Enhanced Raman Spectroscopy Performance of Ag Nanoparticle-Embedded Silica Nanoparticles as Tagging Materials.

Surface-enhanced Raman spectroscopy (SERS) tagging using silica(SiO2)@Ag nanoparticles (NPs) is easy to handle and is being studied in various fields, including SERS imaging and immunoassays. This is primarily due to its structural advantages, characterized by high SERS activity. However, the Ag NPs introduced onto the SiO2 surface may undergo structural transformation owing to the Ostwald ripening phenomenon under various conditions. As a result, the consistency of the SERS signal decreases, reducing their usability as SERS substrates. Until recently, research has been actively conducted to improve the stability of single Ag NPs. However, research on SiO2@Ag NPs used as a SERS-tagging material is still lacking. In this study, we utilized a Raman labeling compound (RLC) to prevent the structural deformation of SiO2@Ag NPs under various conditions and proposed excellent SiO2@Ag@RLC-Pre NPs as a SERS-tagging material. Using various RLCs, we confirmed that 4-mercaptobenzoic acid (4-MBA) is the RLC that maintains the highest stability for 2 months. These results were also observed for the SiO2@Ag NPs, which were unstable under various pH and temperature conditions. We believe that SERS tags using SiO2@Ag NPs and 4-MBA can be utilized in various applications on based SERS because of the high stability and consistency of the resulting SERS signal.

Capture of single Ag atoms through high-temperature-induced crystal plane reconstruction

The “terminal hydroxyl group anchoring mechanism” has been studied on metal oxides (Al2O3, CeO2) as well as a variety of noble and transition metals (Ag, Pt, Pd, Cu, Ni, Fe, Mn, and Co) in a number of generalized studies, but there is still a gap in how to regulate the content of terminal hydroxyl groups to influence the dispersion of the active species and thus to achieve optimal catalytic performance. Herein, we utilized AlOOH as a precursor for γ-Al2O3 and induced the transformation of the exposed crystal face of γ-Al2O3 from (110) to (100) by controlling the calcination temperature to generate more terminal hydroxyl groups to anchor Ag species. Experimental results combined with AIMD and DFT show that temperature can drive the atomic rearrangement on the (110) crystal face, thereby forming a structure similar to the atomic arrangement of the (100) crystal face. This resulted in the formation of more terminal hydroxyl groups during the high-temperature calcination of the support (Al-900), which can capture Ag species to form single-atom dispersions, and ultimately develop a stable and efficient single-atom Ag-based catalyst.

Separating the Wheat from the Chaff among HLA-DQ Eplets.

In transplantation, anti-HLA Abs, especially targeting the DQ locus, are well-known to lead to rejection. These Abs identified by Luminex single Ag assays recognize polymorphic amino acids on HLA, named eplets. The HLA Eplet Registry included 83 DQ eplets, mainly deduced from amino acid sequence alignments, among which 66 have not been experimentally verified. Because eplet mismatch load may improve organ allocation and transplant outcomes, it is imperative to confirm the genuine reactivity of eplets to validate this approach. Our study aimed to confirm 29 nonverified eplets, using adsorption of eplet-positive patients' sera on human spleen mononuclear cells and on transfected murine cell clones expressing a unique DQα- and DQβ-chain combination. In addition, we compared the positive beads patterns obtained in the two commercially available Luminex single Ag assays. Among the 29 nonverified DQ eplets studied, 24 were confirmed by this strategy, including the 7 DQα eplets 40E, 40ERV, 75I, 76 V, 129H, 129QS, and 130A and the 17 DQβ eplets 3P, 23L, 45G, 56L, 57 V, 66DR, 66ER, 67VG, 70GT, 74EL, 86A, 87F, 125G, 130R, 135D, 167R, and 185I. However, adsorption results did not allow us to conclude for the five eplets 66IT, 75S, 160D, 175E, and 185T.

Artificial Intelligence-Assisted Multiparameter Size Discrimination of Silver Nanoparticles through Electrochemical Collision.

Single particle collision is an important tool for size analysis at the individual particle level; however, due to complex dynamic behaviors of nanoparticles on the surface of an electrode, the accuracy of size discrimination is limited. A silver (Ag) nanoparticle (NP) was chosen as the research target, and the dynamic behavior of Ag NPs was simplified by enhancing adsorption between Ag NP and Au ultramicroelectrode (UME) in alkaline media. Immediately after, accurate dynamic and thermodynamic information on single Ag NP was accurately extracted from collision events, including current intensity, transferred charge, and duration time. On the basis that there were differences between parameters of different-sized Ag NPs, multiparameter size discrimination was proposed, which improved the accuracy compared to single-parameter discrimination. More intriguingly, multiparameter analysis was combined with artificial intelligence, a tool adept at processing multidimensional data, for the first time. Finally, artificial intelligence-assisted multiparameter size discrimination was successfully used to intelligently distinguish mixed Ag NPs, with an optimal accuracy of more than 95%. To sum up, the artificial intelligence-assisted multiparameter method showed an excellent ability to quickly achieve the most accurate size discrimination of nanoparticles at the level of individual particle and provide an effective guidance for the application of nanoparticles.

Ferroelectric Polarization and Single-Atom Catalyst Synergistically Promoting CO2 Photoreduction of CuBiP2Se6.

Further improving the activity and selectivity of photocatalytic CO2 reduction remains a challenge. Herein, we propose a new strategy for synergistically promoting photocatalytic CO2 reduction by combining two-dimensional (2D) ferroelectric polarization and single-atom catalysis. Our calculations showed that the ferroelectric polarization of CuBiP2Se6 provides the internal driving force for the separation and migration of photogenerated carriers, which provides a prerequisite for enhancing the photocatalytic efficiency. In addition, the introduction of single Ag atoms can act as an electron reservoir to significantly modify the bonding configurations on the surface through proper static electron transfer, thus effectively promoting the adsorption and activation of CO2 molecules. More importantly, we found that switching the ferroelectric polarization can synergistically optimize the limiting potential as well as control the final products. This study provides a new approach for enhancing the catalytic activity and selectivity of photocatalytic CO2 reduction.

Ab initio morphology prediction of Pd, Ag, Au, and Pt nanoparticles on (0001) sapphire substrates

We energetically predict the morphology of Pd, Ag, Au, and Pt nanoparticles on (0001) sapphire substrates, using density functional theory (DFT) simulations and the well-known Young–Dupre equation. In all cases, the contact angles exceed 90°, indicating that the nanoparticles are spherical. Notably, Au nanoparticles exhibit a higher contact angle than those of their counterparts. The validity of the proposed abinitio nanoparticle morphology prediction approach based on DFT simulations was assessed in comparison with our previous experimental findings pertaining to the time variation of the full width at half maximum (FWHM) of the resonant peak. Furthermore, the diffusivities of single Pd, Ag, Au, and Pt atoms on the substrate were evaluated by calculating the activation energy, offering insights into the underlying physics governing the timing of FWHM peaks. The analysis confirms a higher diffusivity of Au and Ag compared with Pd and Pt. According to the comparison between DFT and experiment results, although no clear relation is observed between the contact angles and timing of FWHM peaks, the diffusivity of sputtered atoms may influence the timing of FWHM peaks. Thus, timing can help to clarify the nanoparticle size, rather than shape.

Raman characteristics of graphene/quartz and graphene/Ag nanoparticles/quartz substrate: Laser power dependence

The sensitivity of graphene surface to adjacent conditions plays an important role that modifies the performance and characteristics of graphene devices working under ambient conditions. Quartz is a dielectric transparent material with excellent optical transmission and therefore graphene/quartz is widely used in graphene device technology. Here, graphene/quartz and graphene/plasmonic nanoparticle/quartz structures were investigated using Raman spectroscopy for applications in nanotechnology like graphene quartz fiber (GQF) multifunctional electrode. Optically induced shift of the Fermi level of graphene monolayer on quartz substrates and on Ag nanoparticles (NPs) distributed on quartz substrates was tracked by increasing the applied laser power. Strained graphene attached to quartz substrate, thermal effects, and charge transfer were discussed using the evolution of the G-peak characteristics. Well distributed Ag NPs on quartz substrate are shown by scanning electron microscopy; an interesting property of plasmonic nanoparticles on quartz substrates. The graphene on single Ag NP verified using Raman mapping images by the surface enhanced Raman G-peak on the Ag NP. The Ag NP was driven to the plasmonic resonance by selecting the laser probe wavelength and the localized surface plasmons excited in Ag NPs were inferred by the transmission and photoluminescence spectra. Investigations of graphene on quartz and on plasmonic nanoparticles/quartz substrates can help for GQF hybrid structures which combines the enhanced thermal and electrical conductivity of graphene/plasmonic nanoparticles in addition to the extraordinary properties of quartz fibers suitable for sensing applications.

Immunogenicity and protective efficacy of RipA, a peptidoglycan hydrolase, against Mycobacterium tuberculosis Beijing outbreak strains

Given that individuals with latent tuberculosis (TB) infection represent the major reservoir of TB infection, latency-associated antigens may be promising options for development of improved multi-antigenic TB subunit vaccine. Thus, we selected RipA, a peptidoglycan hydrolase required for efficient cell division of Mycobacterium tuberculosis (Mtb), as vaccine candidate. We found that RipA elicited activation of dendritic cells (DCs) by induction of phenotypic maturation, increased production of inflammatory cytokines, and prompt stimulation of MAPK and NF-κB signaling pathways. In addition, RipA-treated DCs promoted Th1-polarzied immune responses of naïve CD4+ T cells with increased proliferation and activated T cells from Mtb-infected mice, which conferred enhanced control of mycobacterial growth inside macrophages. Moreover, mice immunized with RipA formulated in GLA-SE adjuvant displayed remarkable generation of Ag-specific polyfunctional CD4+ T cells in both lung and spleen. Following an either conventional or ultra-low dose aerosol challenges with 2 Mtb Beijing clinical strains, RipA/GLA-SE-immunization was not inferior to BCG by mediating protection as single Ag. Collectively, our findings highlighted that RipA could be a novel candidate as a component of multi-antigenic TB subunit vaccines.

Electrocatalytic Reduction of Benzyl Bromide during Single Ag Nanoparticle Collisions.

Previous reports of the electrocatalytic activity of Ag nanoparticles (AgNPs) toward the reduction of organic halides have been limited to measurements of immobilized nanoparticle ensembles. Here, we have investigated the electrochemical reduction of benzyl bromide (PhCH2Br) occurring at single AgNPs (4.2 to 37 nm radius) in methanol, where the effects of nanoparticle size on catalytic behavior can be more thoroughly examined and rigorously quantified. AgNP collisions at a 6.3 μm radius Au ultramicroelectrode (UME) result in measurable electrocatalytic amplification currents from the reduction of PhCH2Br, where collision events are indicated by a sudden step increase in the reduction current recorded in the current-time trace. The dependence of the height of these steps on the applied potential allowed for an analysis of reaction kinetics based on the Butler-Volmer model, resulting in an estimation of the standard rate constant (k0) as a function of AgNP size. Measured values of k0 range from 4.0 × 10-4 to 8.0 × 10-4 cm/s on AgNPs with radii of 14, 29, and 37 nm, whereas k0 was found to be 6.2 × 10-4 cm/s at a 12.3 μm radius Ag disk UME. The results indicate that the kinetics of PhCH2Br reduction are independent of AgNP size and are similar to the reaction kinetics observed at a Ag UME. The frequency of observed particle collisions was found to be dependent on particle size, where 14 nm radius AgNPs resulted in the highest-frequency collisions. The potential- and size-dependent interactions of AgNPs with the Au UME are discussed in terms of the DLVO theory.

Improved performance of kesterite Cu2ZnSn(S,Se)4 thin film solar cells by Ag/Ge co-doping

Cation doping is an important approach to improve the performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) thin film solar cells. Since different cation dopant has different effects on the defects and crystallization of CZTSSe absorber, it is expected to achieve better device performance via the synergistic effects of double cation co-doping compared with the single cation doping. Herein, we investigated the effects of Ag/Ge co-doping on CZTSSe solar cells by doping Ge in an already optimized Ag-alloyed CZTSSe (ACZTSSe). It is found that incorporating a small amount of Ge can further improve the crystallinity and minority carrier lifetime of ACZTSSe. The low-temperature photoluminescence results reveal that the Ge doping primarily suppressed the SnZn defects in ACZTSSe, thereby further boosting the device performance. However, higher Ge doping concentration can lead to a discontinuous surface morphology, which is believed to be related with the relatively low melting temperature and double-layered structure of ACZTSSe absorber. The deteriorated surface morphology results in photocurrent loss in the near-infrared region and decreased fill factor. As the Ge doping ratio increases, there is a balance between the defects and morphology. A champion power conversion efficiency (PCE), 11.4%, was achieved for the Ag/Ge co-doped CZTSSe solar cells at Ge substitution rate of 3%. Compared with the single Ag doping, the average PCE was further promoted by 0.5% due to Ag/Ge co-doping.

Interfacial microstructure and mechanical properties of Si3N4/Invar joints using Ag–Cu–In–Ti with Cu foil as an interlayer

Abstract Si3N4 and Invar alloy brazed joints were achieved using two types of Ag-based interlayers: a Ag–Cu–In–Ti foil and a Ag–Cu–In–Ti/Cu/Ag–Cu multi-interlayer. The results showed that when only using a single Ag–Cu–In–Ti filler, the wave-shaped Fe2Ti + Ni3Ti intermetallic compounds are concentrated in the middle of the brazing seam. When adding Cu as the interlayer, the dissolution of the Cu interlayer formed a large number of Cu(s,s) blocks of different sizes in the brazing seam, which hindered the concentrated distribution of Fe2Ti + Ni3Ti intermetallic compounds in the brazing seam. As a result, Fe2Ti and Ni3Ti were dispersedly distributed in the brazing seam, increasing the shear strength of the brazed joint. The shear strength of brazed joints was increased by 82 % compared to joints brazed with a single Ag–Cu–In–Ti filler when the Cu interlayer was added.

Spotting d-band centers of single-atom catalysts by oxygen intermediate-boosted electrochemiluminescence.

Catalytic activities of single-atom catalysts are strongly dependent on their d-band centers. However, it is a long-standing challenge to provide a cost-effective and accurate evaluation for the positions of d-band centers of these catalysts due to the fact that the widely applicable photoelectron spectroscopy methodologies require complicated sampling and spectral unfolding processes. In this contribution, we have proposed oxygen intermediate-boosted electrochemiluminescence (ECL) for rapid spotting of the d-band centers of single-atom catalysts, involving single atomic Au, Ag, Cu and Fe. It was disclosed that the d-band centers of single-atom catalysts closer to the Fermi level could facilitate the interaction between catalysts and oxygen intermediates, leading to higher luminol ECL intensities as a result of the promoted adsorption and reduction ability towards oxygen intermediates. Moreover, this correlation was also adapted for other metal catalysts such as Au and Ag nanoparticles. This correspondence could be utilized for an accurate identification of d-band centers of single-atom catalysts. It is anticipated that the proposed strategy could be beneficial for a deep understanding of microstructure studies of single-atom catalysts to achieve advanced catalytic performances.