Highly sensitive SERS substrates with a limit of detection in the zeptomole (for Nile blue A and oxazine 720) range were fabricated through a bottom-up strategy. Ag nanoparticles (Ag NPs) were self-assembled onto glass slides by using 3-mercaptopropyltrimethoxysilane (MPTMS) sol–gel as linker. The substrates were characterized by UV-Vis and AFM after each deposition of Ag NPs. It was found that the glass slide presented just a few Ag NPs aggregates scattered throughout the surface after just one deposition. The glass surface was gradually covered by a homogeneous distribution of Ag NPs aggregates as the deposition number increased. Surface-enhanced Raman scattering (SERS) of the substrates was examined at different numbers of Ag NPs deposition using nile blue A and oxazine 720 as probe molecules and two laser excitations (632.8 nm and 785 nm). Optimum SERS was observed after six depositions of Ag NPs. SERS mapping indicated that at lower deposition numbers (less than 3 Ag NPs depositions) the substrates presented a few SERS “hot–spots” randomly distributed at the surface. After 7 Ag NPs depositions, spatial distribution of the SERS signal followed a Gaussian statistics, with a percent relative standard deviation (RSD%) of ∼19%. In addition, the sample-to-sample reproducibility of the SERS intensities under both laser excitations was lower than 20%. It was also found that these substrates can provide giant Raman signal enhancement. At optimum conditions and with a 632.8 nm laser, the signal from an estimated of only ∼44 probe molecules (100× objective) can still be detected.

Although superhydrophobic porous membranes are considered to be very promising candidates for oil–water separation, their fabrication methods often involve complicated treatments to build a coating with micro/nano-features on a porous mesh (called “coating on a mesh structure”), which can lead to weak mechanical stability of the superhydrophobic surfaces and the formation of inhomogeneous membrane pores. Herein, we report a facile and environmentally friendly 3D printing approach to fabricate superhydrophobic membranes with an ordered porous structure for oil–water separation using hydrophobic nanosilica-filled polydimethylsiloxane (PDMS) ink. The addition of nanosilica can improve the mechanical strength of the ink and thus ensures the formation of desired topographical structures without the risk of collapsing during 3D printing. Through adjusting the geometrical parameters, a superhydrophobic PDMS membrane was obtained, which mainly depended on the roughness at the sub-millimeter scale. More importantly, the 3D printing approach described herein integrated the superhydrophobic surface into the porous framework and resulted in a mechanically durable superhydrophobic membrane, which successfully avoids the weak interface adhesion issue that arises from the traditional “coating on a mesh structure.” Moreover, the pore size of the printed membrane could be easily adjusted via a computer program to optimize both the liquid flux and separation efficiency of the membranes. The maximum oil–water separation efficiency (∼99.6%) could be achieved for the printed porous membrane with the pore size of 0.37 mm, which also exhibited a high flux of ∼23 700 L m⁻² h⁻¹.

Surface-enhanced Raman scattering (SERS) from molecular probes adsorbed on Au:Ag bimetallic nanoparticles with various compositions was investigated. Au:Ag bimetallic nanoparticles (NPs), with the diameters between 3–5 nm, were prepared and characterized by HRTEM and UV-Vis absorption. Their SERS properties were examined by using four different probe molecules, and compared with NPs made of pure Au or Ag. It is found that the SERS property of the alloy NPs is not only dependent on the Au:Ag ratio of the bimetallic NPs, but also on the chemical nature of the SERS probe. For the two positively charged SERS probes, oxazine 720 (Oxa) and Nile Blue A (NBA), the alloy NPs with higher Au content provided the largest SERS signal. However, for the probes 4-hydroxythiophenol (HTP) and thiophenol (TP), the best SERS performance was obtained for the highest Ag ratio. DFT calculations indicated a charge-transfer between Au and Ag atoms in the alloys, creating positively charged domains rich in Ag atom, and negatively charge regions dominated by Au atoms. It is proposed that the probe-specific enhancement is related to the selective binding of probe molecules to the partially charged surface domains in the alloys. Our results suggest that SERS substrate optimizations based on bimetallic nanoparticles should consider the nature of the probes and the electronic-induced effects from the alloys.