Search Results (79)

The detection of trace chemicals at low and ultra-low concentrations is critical for applications in environmental monitoring, medical diagnostics, food safety and other fields. Conventional detection techniques often lack the required sensitivity, specificity, or cost-effectiveness, making real-time, in situ analysis challenging. Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical tool, offering improved sensitivity through the enhancement of Raman scattering by plasmonic nanostructures. While noble metals such as Ag and Au are currently the reference choices for SERS substrates, fabrication methods should balance enhancement efficiency, reproducibility and scalability. In this study, we propose a novel approach for SERS substrate fabrication using reactive Aerosol Jet Printing (r-AJP) as an innovative additive manufacturing technique. The r-AJP process enables in-flight Ag seed reduction and nucleation of Ag nanoparticles (NPs) by mixing silver nitrate and ascorbic acid aerosols before deposition, as suggested by computational fluid dynamics (CFD) simulations. The resulting coatings were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses, revealing the formation of nanoporous crystalline Ag agglomerates partially covered by residual matter. The as-prepared SERS substrates exhibited remarkable SERS activity, demonstrating a high enhancement factor (10⁶) for rhodamine (R6G) detection. Our findings highlight the potential of r-AJP as a scalable and cost-effective fabrication strategy for next-generation SERS sensors, paving the way for the development of a new additive manufacturing tool for noble metal material deposition. Full article

Electrochemical nitrogen reduction reaction (NRR) has emerged as a promising approach for sustainable ammonia synthesis under ambient conditions, offering a low-energy alternative to the traditional Haber–Bosch process. However, the development of efficient and sustainable electrocatalysts for NRR remains a significant challenge. Noble metals, known for their exceptional chemical stability under electrocatalytic conditions, have garnered considerable attention in this field. In this study, we report the successful synthesis of nanoporous CuAuPtPd quasi-high-entropy alloy (quasi-HEA) prism arrays through “melt quenching” and “dealloying” techniques. The as-obtained alloy demonstrates remarkable performance as an NRR electrocatalyst, achieving an impressive ammonia synthesis rate of 17.5 μg h⁻¹ mg⁻¹ at a potential of −0.2 V vs. RHE, surpassing many previously reported NRR catalysts. This work not only highlights the potential of quasi-HEAs as advanced NRR electrocatalysts but also provides valuable insights into the design of nanoporous multicomponent materials for sustainable energy and catalytic applications. Full article

Nanoporous metals have garnered significant attention in catalysis due to their unique three-dimensional interconnected network structure and pronounced localized surface plasmon resonance (LSPR) properties. In this study, nanoporous Au–Ag shells with varying pore sizes (8, 10, 12, and 18 nm) were synthesized, and their catalytic efficiencies were systematically evaluated. The conversion of p-nitrothiophenol (PNTP) to dimercapto-azobenzene (DMAB) was used to investigate the influence of pore size on the reaction kinetics and surface-enhanced Raman scattering (SERS) effects. Experimental results reveal that the nanoporous Au–Ag shells with a 12 nm pore size exhibit relatively high catalytic efficiency. Furthermore, tuning the pore size enables the modulation of LSPR in the near-infrared region. These findings highlight the critical role of pore size modulation in determining the photocatalytic performance of nanoporous metallic materials and provide valuable insights for the design and optimization of highly efficient photocatalysts. Full article

Preeclampsia is a pregnancy-specific hypertensive syndrome recognized as the leading cause of maternal and fetal morbidity worldwide. Early diagnosis is crucial for mitigating its adverse effects, and recent investigations have identified endoglin as a potential biomarker for this purpose. Here, we present the development of a hybrid biosensor platform for the ultrasensitive detection of endoglin, aimed at enabling the early diagnosis of preeclampsia. This platform integrates the high surface area properties of nanoporous anodic alumina (NAA) with the unique optical characteristics of gold nanoclusters (AuNCs) to achieve enhanced detection capabilities. The NAA surface functionalized to promote attachment of AuNCs, which then was functionalized with specific antibodies to confer selectivity towards endoglin. Photoluminescence (PL) analysis of the biosensor demonstrated a linear detection range of 10–50 ng/mL, with a detection limit of 5.4 ng/mL and a sensitivity of 0.004 a.u./(ng/mL). This proof-of-concept study suggests that the NAA-AuNCs-based biosensing platform holds significant potential for the development of ultrasensitive, portable, and cost-effective diagnostic tools for preeclampsia, offering a promising avenue for advancing prenatal care. Full article

In this work, a novel formaldehyde sensor was constructed based on nanoporous, flower-like, Pb-containing Pd–Au nanoparticles deposited on the cathode in a double-cabin galvanic cell (DCGC) with a Cu plate as the anode, a multiwalled carbon nanotube-modified glassy carbon electrode as the cathode, a 0.1 M HClO₄ aqueous solution as the anolyte, and a 3.0 mM PdCl₂ + 1.0 mM HAuCl₄ + 5.0 mM Pb(ClO₄)₂ + 0.1 M HClO₄ aqueous solution as the catholyte, respectively. Electrochemical studies reveal that the stripping of bulk Cu can induce underpotential deposition (UPD) of Pb during the galvanic replacement reaction (GRR) process, which affects the composition and morphology of Pb-containing Pd–Au nanoparticles. The electrocatalytic activity of Pb-containing nanoparticles toward formaldehyde oxidation was examined in an alkaline solution, and the experimental results showed that formaldehyde mainly caused direct oxidation on the surface of Pb-containing Pd–Au nanoparticles while inhibiting the formation of CO poison to a large degree. The proposed formaldehyde sensor exhibits a linear amperometric response to formaldehyde concentrations from 0.01 mM to 5.0 mM, with a sensitivity of 666 μA mM⁻¹ cm⁻², a limit of detection (LOD) of 0.89 μM at triple signal-to-noise, rapid response, high anti-interference ability, and good repeatability. Full article

Nanoporous gold (np-Au) has found its use in applications ranging from catalysis to biosensing, where pore morphology plays a critical role in performance. While the morphology evolution of bulk np-Au has been widely studied, knowledge about its thin-film form is limited. This work hypothesizes that the mechanical compliance of the thin film substrate can play a critical role in the morphology evolution. Via experimental and finite-element-analysis approaches, we investigate the morphological variation in np-Au thin films deposited on compliant silicone (PDMS) substrates of a range of thicknesses anchored on rigid glass supports and compare those to the morphology of np-Au deposited on glass. More macroscopic (10 s to 100 s of microns) cracks and discrete islands form in the np-Au films on PDMS compared to on glass. Conversely, uniformly distributed microscopic (100 s of nanometers) cracks form in greater numbers in the np-Au films on glass than those on PDMS, with the cracks located within the discrete islands. The np-Au films on glass also show larger ligament and pore sizes, possibly due to higher residual stresses compared to the np-Au/PDMS films. The effective elastic modulus of the substrate layers decreases with increasing PDMS thickness, resulting in secondary np-Au morphology effects, including a reduction in macroscopic crack-to-crack distance, an increase in microscopic crack coverage, and a widening of the microscopic cracks. However, changes in the ligament/pore widths with PDMS thickness are negligible, allowing for independent optimization for cracking. We expect these results to inform the integration of functional np-Au films on compliant substrates into emerging applications, including flexible electronics. Full article

Nanoporous (NP) gold, the most extensively studied and efficient NP metal, possesses exceptional properties that make it highly attractive for advanced technological applications. Notably, its remarkable catalytic properties in various significant reactions hold enormous potential. However, the exploration of its catalytic activity in the degradation of water pollutants remains limited. Nevertheless, previous research has reported the catalytic activity of NP Au in the degradation of methyl orange (MO), a toxic azo dye commonly found in water. This study aims to investigate the behavior of nanoporous gold in MO solutions using UV-Vis absorption spectroscopy and high-performance liquid chromatography. The NP Au was prepared by chemical removal of silver atoms of an AuAg precursor alloy prepared by ball milling. Immersion tests were conducted on both pellets and powders of NP Au, followed by examination of the residual solutions. Additionally, X-ray photoelectron spectroscopy and electrochemical impedance measurements were employed to analyze NP Au after the tests. The findings reveal that the predominant and faster process involves the partially reversible adsorption of MO onto NP Au, while the catalytic degradation of the dye plays a secondary and slower role in this system. Full article

Plasmonic metallic nanoparticles, like Au, can be used to tune the optical properties of photonic nanoarchitectures occurring in butterfly wing scales possessing structural color. The effect of the nanoscale Au depends on the location and the amount deposited in the chitin-based photonic nanoarchitecture. The following three types of Au introduction methods were compared regarding the structural and optical properties of the resulting hybrid bio-nanocomposites: (i) growth of Au nanoparticles inside the nanopores of butterfly wing scales by a light-induced in situ chemical reduction of HAuCl₄ in aqueous solution containing sodium citrate, as a new procedure we have developed, (ii) drop-drying of the aqueous Au sol formed during procedure (i) in the bulk liquid phase, and (iii) physical vapor deposition of Au thin film onto the butterfly wing. We investigated all three methods at two different Au concentrations on the wings of laboratory-bred blue-colored male Polyommatus icarus butterflies and characterized the optical properties of the resulting hybrid bio-nanocomposites. We found that the drop-drying and the in situ growth produced comparable redshift in the spectral position of the reflectance maximum associated with the chitin-based photonic nanoarchitecture in the wing scales, while the 5 nm or 15 nm thick Au layers vacuum deposited onto the butterfly wing behaved like an optical filter, without inducing spectral shift. The in situ growth in the photonic nanoarchitecture under intense illumination produced uniform Au nanoparticles located in the pores of the biological template, which is more advantageous for further applications. An additional benefit of this method is that the Au nanoparticles do not aggregate on drying, like in the case of drop-drying of preformed Au nanoparticles from the citrate-stabilized sol. Full article

Compared to traditional actuators (such as piezoelectric ceramics), metal actuators possess the advantages of a low energy consumption, large strain amplitude, and high strain energy density. However, most of the existing metal actuators with an excellent comprehensive performance are composed of precious metals, which are limited by high costs and have almost no possibility for large-scale production in the future. This study focuses on non-precious metal materials and exploits a one-step chemical dealloying method to prepare bulk nanoporous (NP) CoCuAl actuators (NP-CCA) from Al₇₀Co₂₀Cu₁₀ alloy. The microstructure and actuation properties of the NP-CCA were analyzed in detail. The dense continuous nanoscale pores provide an excellent network connectivity for a large strain response, enabling the NP-CCA to achieve a strain amplitude of up to 1.19% (more than eight and two times that of NP-Pt and NP-Ag, respectively), comparable to precious metal actuators. In addition, the NP-CCA possesses a high strain energy density, which is prominent in many precious metal actuation materials (such as NP-Au, NP-Ag, and NP-Pt). Full article

In this study, anodic aluminum oxide membranes (AAOMs) and Au-coated AAOMs (AAOM/Au) with pore diameters of 55 nm and inter-pore spacing of 100 nm are used to develop ZnO/AAOM and ZnO/ZnAl₂O₄/Au nanoarrays of different morphologies. The effects of the electrodeposition current, time, barrier layer, and Au coating on the morphology of the resultant nanostructures were investigated using field emission scanning electron microscopy. Energy dispersive X-ray and X-ray diffraction were used to analyze the structural parameters and elemental composition of the ZnO/ZnAl₂O₄/Au nanoarray, and the Kirkendall effect was confirmed. The developed ZnO/ZnAl₂O₄/Au electrode was applied to remove organic dyes from aqueous solutions, including methylene blue (MB) and methyl orange (MO). Using a 3 cm² ZnO/ZnAl₂O₄/Au sample, the 100% dye removal for 20 ppm MB and MO dyes at pH 7 and 25 °C was achieved after approximately 50 and 180 min, respectively. According to the kinetics analysis, the pseudo-second-order model controls the dye adsorption onto the sample surface. AAOM/Au and ZnO/ZnAl₂O₄/Au nanoarrays are also used as pH sensor electrodes. The sensing capability of AAOM/Au showed Nernstian behavior with a sensitivity of 65.1 mV/pH (R² = 0.99) in a wide pH range of 2–9 and a detection limit of pH 12.6, whereas the ZnO/ZnAl₂O₄/Au electrode showed a slope of 40.1 ± 1.6 mV/pH (R² = 0.996) in a pH range of 2–6. The electrode’s behavior was more consistent with non-Nernstian behavior over the whole pH range under investigation. The sensitivity equation was given by V(mV) = 482.6 + 372.6 e^{−0.2095 pH} at 25 °C with R² = 1.0, which could be explained in terms of changes in the surface charge during protonation and deprotonation. Full article

High-resolution nanotransfer printing (nTP) technologies have attracted a tremendous amount of attention due to their excellent patternability, high productivity, and cost-effectiveness. However, there is still a need to develop low-cost mold manufacturing methods, because most nTP techniques generally require the use of patterned molds fabricated by high-cost lithography technology. Here, we introduce a novel nTP strategy that uses imprinted metal molds to serve as an alternative to a Si stamp in the transfer printing process. We present a method by which to fabricate rigid surface-patterned metallic molds (Zn, Al, and Ni) based on the process of direct extreme-pressure imprint lithography (EPIL). We also demonstrate the nanoscale pattern formation of functional materials, in this case Au, TiO₂, and GST, onto diverse surfaces of SiO₂/Si, polished metal, and slippery glass by the versatile nTP method using the imprinted metallic molds with nanopatterns. Furthermore, we show the patterning results of nanoporous crossbar arrays on colorless polyimide (CPI) by a repeated nTP process. We expect that this combined nanopatterning method of EPIL and nTP processes will be extendable to the fabrication of various nanodevices with complex circuits based on micro/nanostructures. Full article

The electrochemical reduction of CO₂ to value-added chemicals renewable electricity is a promising and ecofriendly strategy to achieve the national strategic goal of “carbon peak and carbon neutrality” and solve the greenhouse effect. Due to the variety of products in CO₂ electroreduction (CO₂ER), catalytic selectivity has become a key factor in the design of electrode structure. Herein, a systematic investigation of CO₂ER on the nanoporous gold films with different thicknesses prepared by the self-deposition method developed by ourselves. Mass transfer effects are found to play an important role in determining product selectivity and activity. The specific activity for CO evolution (j_CO) with exponential declination has more dramatic tendency than the specific activity for hydrogen evolution (j_H2) with linear decay with increasing nanoporous gold film thickness. Different from the behaviors within the mesoporous structures in previous studies, the retarded transport of HCO₃⁻ ions within the nanoscale pores is more sensitive than that of protons. This phenomenon implies the necessity of considering mass transfer effects in the design of outstanding electrocatalysts for CO₂ER as well as for understanding the geometrical infrastructure-performance relationships. Full article

Applying the surface-enhanced Raman scattering (SERS) method to detect bioactive molecules such as DNA, proteins, and drugs has significant potential for structure-sensitive nondestructive chemical analysis. The SERS discrimination of single-molecule oligomers in DNA, microRNA, and proteins has attracted wide attention due to the possibility of developing new sensing technology. The collected signal’s sensitivity has the level of detection of single oligomers, which can be compared with the simulation results corresponding to the sensor structure. We investigate the averaging method of the individual bond spectra for DNA nucleotides in the ring part of the pyrimidine (6-ring) and purine (6–5-ring) bases to form vibrational spectra obtained by molecular dynamics (MD) simulation. The system consists of the Au nanoparticles (from 1 to 4 NP assay) attached to a graphene sheet at the edge of the nanopore that localizes in the nanopore nucleotide interaction and spectral enhancement. The nucleotide translocation velocity set at 0.025 m/s compares with the experimental range. The vibrational spectra ring average has been tested for adenine and guanine with close correspondence (in the 500–1700 cm⁻¹ range) to the experimental Raman and SERS spectra and extended to cytosine and thymine nucleotides. We also modified the number of the Au nanoparticles from one NP to four identical NPs to evaluate the influence of the interaction on the MD transient spectra. The variations of mode frequencies and amplitudes due to the number of Au NPs in bond spectra, as well as ring averages, mark the corresponding Au–nucleotide interactions and are considered for use as training sets for machine learning methods. Full article

Preparation of a high-sensitive and uniform surface-enhanced Raman spectroscopy (SERS) active substrate structure usually faces complex processes and high costs. Here, porous Au–Ag composite nanostructures that are conventional fabricated by the deposition of a multilayer Au–Ag, annealing, and dealloying process are proposed for high-performance SERS. By annealing at a suitable temperature, nanopores could be firmly distributed on the surface, which serves as hot spots. The electric field distribution was also performed by the finite difference time domain. The experiment results exhibited excellent uniformity and high sensitivity of SERS detection. The enhancement factor of the R6G molecules detected by the SERS substrate reached 1.37 × 10⁷, and the relative standard deviation was as low as 4.9%. The minimum detection concentration of R6G molecules by the Au–Ag composite nanostructures with bottom Au mirror could reach 10⁻¹³ M. The proposed Au–Ag composite nanostructures and the fabrication process have great potential in preparation of a high-sensitive and uniform SERS substrate. Full article

Nanoporous Au (NPG) prepared by dealloying is one of the most used substrates for surface-enhanced Raman scattering (SERS). The morphology tailoring of the NPG to obtain both ultrafine pores and suitable Au/Ag ratio is of great importance for the acquiring of enhanced SERS performance. Compared with the chemical dealloying, the electrochemical dealloying can tailor the NPG to be more flexible by the additional adjustment of dealloying voltage and current. Thus, further understanding on the morphology evolution of NPG during the electrochemical dealloying to obtain enhanced SERS performance is of great importance. In the presented work, the morphology and composition evolution of the NPG film during the electrochemical dealloying was investigated. NPG films with a stable pore diameter of approximately 11 nm as well as diverse compositions were obtained by electrochemical dealloying an Au-Ag alloy film. The prepared NPG film exhibits an enhanced SERS activity with an enhancement factor (EF) of 7.3 × 10⁶ and an excellent detection limit of 10⁻⁹ M. This work provides insights into the morphology and composition evolution of the NPG during the electrochemical dealloying process to obtain enhanced SERS performance. Full article