The galvanic replacement reaction is a highly versatile approach for the creation of a variety of nanostructured materials. However, the majority of reports are limited to the replacement of metallic nanoparticles or metal surfaces. Here we extend this elegant approach and describe the galvanic replacement of the liquid metal alloy galinstan with Ag and Au. This is achieved at a macrosized droplet to create a liquid metal marble that comprises a liquid metal core and a solid metal shell, whereby the morphology of the outer shell is determined by the concentration of metallic ions used in the solution during the galvanic replacement process. In principle, this allows one to recover precious metal ions from solution in their metallic form, which are immobilized on the liquid metal and therefore easy to recover. The reaction is also undertaken at liquid metal microdroplets created via sonication to produce Ag- and Au-based galinstan nanorice particles. These materials are characterized with SEM, XRD, TEM, SAED, EDX, XPS, UV-visible spectroscopy, and open-circuit potential versus time experiments to understand the galvanic replacement process. Finally, the nanosized materials are investigated for their catalytic activity toward the reduction of methylene blue in the presence of sodium borohydride. This approach illustrates a new avenue of research for the galvanic replacement process and, in principle, could be applied to many more systems.
A facile route to prepare catalytically active materials from a galinstan liquid metal alloy is introduced. Sonicating liquid galinstan in alkaline solution or treating it in reducing media results in the creation of solid In/Sn rich microspheres that show catalytic activity toward both potassium ferricyanide and 4-nitrophenol reduction.
Sensors to detect toxic and harmful gases are usually based on metal oxides that are operated at elevated temperature. However, enabling gas detection at room temperature (RT) is a significant ongoing challenge. Here, we address this issue by demonstrating that microrods of semiconducting CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) with nanostructured features can be employed as conductometric gas sensors operating at 50 °C for detection of oxidizing and reducing gases such as NO 2 and NH 3 . The sensor is evaluated at RT and up to 200 °C. It was found that CuTCNQ is transformed into a N-doped CuO material with p-type conductivity when annealed at the maximum temperature. This is the first time that such a transformation, from a semiconducting charge transfer material into a N-doped metal oxide, is detected. It is shown here that both the surface chemistry and the type of majority charge carrier within the sensing layer are critically important for the type of response toward oxidizing and reducing gases. A detailed physical description of the NO 2 and NH 3 sensing mechanism at CuTCNQ and N-doped CuO is provided to explain the differences in the response. For the N-doped CuO sensor, detection limits of 1 ppm for NO 2 and 10 ppm for NH 3 are achieved.
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