Plasmonic MOF thin films with raman standard for fast and ultrasensitive SERS detection of chemical warfare agents in ambient air

Lafuente, Marta ; De Marchi, Sarah ; Urbiztondo, Miguel ; Pastoriza-Santos, Isabel ; Perez-Juste, Ignacio ; Santamaria, Jesús (Universidad de Zaragoza) ; Mallada, Reyes (Universidad de Zaragoza) ; Pina, María (Universidad de Zaragoza)

Resumen: Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique for selective detection and quantification of molecules at extremely low concentrations. However, practical SERS applications for gaseous chemicals with small cross section is still in its early stages. We herein report a plasmonic-sorbent thin-film platform with integrated Raman internal standard with outstanding SERS sensing capabilities for chemical warfare agents (CWA) simulants. The thin film is constituted of close-packed core–shell Au@Ag nanorods individually encapsulated within a ZIF-8 framework (Au@Ag@ZIF-8). While the Au@Ag nanoparticles amplify the Raman signal of molecules located near their surface, the ZIF-8 framework plays a key role in the trapping of the dimethyl methylphosphonate (DMMP) or 2-chloroethyl ethyl sulfide (CEES) from the gas phase as well as Raman internal standard. The underlying adsorption mechanism of the molecules within the ZIF-8 framework as well as the interaction between DMMP and Ag surface are investigated by computational simulations. Outstanding SERS sensing capabilities of Au@Ag@ZIF-8 thin films, in terms of response time, quantification limit, reproducibility, and recyclability, are demonstrated for dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES), selected as CWA simulants of sarin gas and mustard gas, respectively. A limit of detection (LOD) of 0.2 ppbV is reported for DMMP. Additionally, experiments performed with portable Raman equipment detect 2.5 ppmV for DMMP in ambient air and 76 ppbV for CEES in N2, with response times of 21 and 54 s, respectively. This proof of concept opens the door for handheld SERS-based gas sensing at ultralow concentrations in practical applications, such as homeland security, critical infrastructure protection, chemical process monitoring, or personalized medicine.

Idioma: Inglés

DOI: 10.1021/acssensors.1c00178

Año: 2021

Publicado en: ACS Sensors 6, 6 (2021), 2241–2251
ISSN: 2379-3694

Factor impacto JCR: 9.618 (2021)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 26 / 180 = 0.144 (2021) - Q1 - T1
Categ. JCR: CHEMISTRY, ANALYTICAL rank: 5 / 87 = 0.057 (2021) - Q1 - T1
Categ. JCR: NANOSCIENCE & NANOTECHNOLOGY rank: 26 / 109 = 0.239 (2021) - Q1 - T1

Factor impacto CITESCORE: 12.2 - Chemical Engineering (Q1) - Physics and Astronomy (Q1)

Factor impacto SCIMAGO: 1.833 - Bioengineering (Q1) - Process Chemistry and Technology (Q1) - Fluid Flow and Transfer Processes (Q1)

Financiación: info:eu-repo/grantAgreement/EC/H2020/883390/EU/Advanced Surface Enhanced Raman Spectroscopy (SERS) based technologies for gas and liquids sensING in the area of chemical protection/SERSing
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-79419-R
Financiación: info:eu-repo/grantAgreement/ES/MINECO/MAT2016-77809-R

Tipo y forma: Article (Published version)

Área (Departamento): Área Ingeniería Química (Dpto. Ing.Quím.Tecnol.Med.Amb.)