Significantly Accelerated Photochemical Perfluorooctanoic Acid Decomposition at the Air-Water Interface of Microdroplets.

The efficient elimination of per- and polyfluoroalkyl substances (PFASs) from the environment remains a huge challenge and requires advanced technologies. Herein, we demonstrate that perfluorooctanoic acid (PFOA) photochemical decomposition could be significantly accelerated by simply carrying out this process in microdroplets. The almost complete removal of 100 and 500 µg/L PFOA was observed after 20 min of irradiation in microdroplets, while this was achieved after about 2 h in the corresponding bulk phase counterpart. To better compare the defluorination ratio, 10 mg/L PFOA was used typically, and the defluorination rates in microdroplets were tens of times faster than that in the bulk phase reaction system. The high performances in actual water matrices, universality, and scale-up applicability were demonstrated as well. We revealed in-depth that the great acceleration is due to the abundance of the air-water interface in microdroplets, where the reactants concentration enrichment, ultrahigh interfacial electric field, and partial solvation effects synergistically promoted photoreactions responsible for PFOA decomposition, as evidenced by simulated Raman scattering microscopy imaging, vibrational Stark effect measurement, and DFT calculation. This study provides an effective approach and highlights the important roles of air-water interface of microdroplets in PFASs treatment.

Automatic Identification of Individual Nanoplastics by Raman Spectroscopy Based on Machine Learning.

The increasing prevalence of nanoplastics in the environment underscores the need for effective detection and monitoring techniques. Current methods mainly focus on microplastics, while accurate identification of nanoplastics is challenging due to their small size and complex composition. In this work, we combined highly reflective substrates and machine learning to accurately identify nanoplastics using Raman spectroscopy. Our approach established Raman spectroscopy data sets of nanoplastics, incorporated peak extraction and retention data processing, and constructed a random forest model that achieved an average accuracy of 98.8% in identifying nanoplastics. We validated our method with tap water spiked samples, achieving over 97% identification accuracy, and demonstrated the applicability of our algorithm to real-world environmental samples through experiments on rainwater, detecting nanoscale polystyrene (PS) and polyvinyl chloride (PVC). Despite the challenges of processing low-quality nanoplastic Raman spectra and complex environmental samples, our study demonstrated the potential of using random forests to identify and distinguish nanoplastics from other environmental particles. Our results suggest that the combination of Raman spectroscopy and machine learning holds promise for developing effective nanoplastic particle detection and monitoring strategies.

Imaging of pH distribution inside individual microdroplet by stimulated Raman microscopy.

Aerosol microdroplets as microreactors for many important atmospheric reactions are ubiquitous in the atmosphere. pH largely regulates the chemical processes within them; however, how pH and chemical species spatially distribute within an atmospheric microdroplet is still under intense debate. The challenge is to measure pH distribution within a tiny volume without affecting the chemical species distribution. We demonstrate a method based on stimulated Raman scattering microscopy to visualize the three-dimensional pH distribution inside single microdroplets of varying sizes. We find that the surface of all microdroplets is more acidic, and a monotonic trend of pH decreasing is observed in the 2.9-µm aerosol microdroplet from center to edge, which is well supported by molecular dynamics simulation. However, bigger cloud microdroplet differs from small aerosol for pH distribution. This size-dependent pH distribution in microdroplets can be related to the surface-to-volume ratio. This work presents noncontact measurement and chemical imaging of pH distribution in microdroplets, filling the gap in our understanding of spatial pH in atmospheric aerosol.

Dense Arrays of Nanohelices: Raman Scattering from Achiral Molecules Reveals the Near-Field Enhancements at Chiral Metasurfaces.

Against the background of the current healthcare and climate emergencies, surface enhanced Raman scattering (SERS) is becoming a highly topical technique for identifying and fingerprinting molecules, e.g., within viruses, bacteria, drugs, and atmospheric aerosols. Crucial for SERS is the need for substrates with strong and reproducible enhancements of the Raman signal over large areas and with a low fabrication cost. Here, dense arrays of plasmonic nanohelices (≈100 nm in length), which are of interest for many advanced nanophotonics applications, are investigated, and they are shown to present excellent SERS properties. As an illustration, two new ways to probe near-field enhancement generated with circular polarization at chiral metasurfaces are presented, first using the Raman spectra of achiral molecules (crystal violet) and second using a single, element-specific, achiral molecular vibrational mode (i.e., a single Raman peak). The nanohelices can be fabricated over large areas at a low cost and they provide strong, robust and uniform Raman enhancement. It is anticipated that these advanced materials will find broad applications in surface enhanced Raman spectroscopies and material science.

Significantly Accelerated Hydroxyl Radical Generation by Fe(III)-Oxalate Photochemistry in Aerosol Droplets.

Fe(III)-oxalate complexes are ubiquitous in atmospheric environments, which can release reactive oxygen species (ROS) such as H2O2, O•2-, and OH• under light irradiation. Although Fe(III)-oxalate photochemistry has been investigated extensively, the understanding of its involvement in authentic atmospheric environments such as aerosol droplets is far from enough, since the current available knowledge has mainly been obtained in bulk-phase studies. Here, we find that the production of OH• by Fe(III)-oxalate in aerosol microdroplets is about 10-fold greater than that of its bulk-phase counterpart. In addition, in the presence of Fe(III)-oxalate complexes, the rate of photo-oxidation from SO2 to sulfate in microdroplets was about 19-fold faster than that in the bulk phase. The availability of efficient reactants and mass transfer due to droplet effects made dominant contributions to the accelerated OH• and SO42- formation. This work highlights the necessary consideration of droplet effects in atmospheric laboratory studies and model simulations.

Strategies and Challenges of Identifying Nanoplastics in Environment by Surface-Enhanced Raman Spectroscopy.

Nanoplastics (<1000 nm) have been evidenced to be universal in a variety of environmental media. They pose a potential cytotoxicity and health risk due to their tiny size, which allows them to easily penetrate biological barriers and enter cells. Here, we briefly review the various prevalent analytical techniques or tools for identifying nanoplastics, and further move to focus on their advantages and disadvantages. Surface-enhanced Raman spectroscopy (SERS) has been implemented for the identification of individual nanoparticles because of its high sensitivity to molecules and ease of rapid characterization. Therefore, we introduce the SERS technique in the following aspects, (1) principles of SERS; (2) strategies and advances in SERS detection of nanoplastics; and (3) applying SERS to real environmental samples. We put our effort into the summarization of efficient SERS substrates that essentially enable the better detection of nanoplastics, and extend to discuss how the reported nanoplastics pretreatment methodologies can bring SERS analysis to practical applications. A further step moving forward is to investigate the problems and challenges of currently applied SERS detection methods and to look at future research needs in nanoplastics detection employing SERS analysis.

A protocol to study microdroplet photoreaction at an individual droplet level using in situ micro-Raman spectroscopy.

Photochemical synthesis and photocatalysis in droplet microreactors represent promising approaches to relieve the global energy and environmental crises. Here, we describe a protocol for studying microdroplet photoreaction at an individual droplet level based on in situ micro-Raman spectroscopy. We provide details of superhydrophobic substrate preparation, microdroplets generation, photoreactions performing, and data analyses. In addition, we show the operational details of preliminary scale-up tests of microdroplet photoreaction for practical application. For complete details on the use and execution of this protocol, please refer to Li et al. (2022).

Ultrasound-boosted selectivity of CO in CO2 electrochemical reduction.

Among the possible products of CO2 electrochemical reduction, CO plays a unique and vital role, which can be an ideal feedstock for further reduction to C2+ products, and also the important component of syngas that can be used as feedstock for value-added chemicals and fuels. However, it is still a challenge to tune the CO selectivity on Cu electrode. Here we newly construct an ultrasound-assisted electrochemical method for CO2 reduction, which can tune the selectivity of CO2 to CO from less than 10% to >80% at -1.18 V versus (vs.) reversible hydrogen electrode (RHE). The partial current density of CO production is significantly improved by 15 times. By in-situ Raman study, the dominating factor for the improved CO production is attributed to the accelerated desorption of *CO intermediate. This work provides a facile method to tune the product selectivity in CO2 electrochemical reduction.

New insights into the role of sulfite in BiOX photocatalytic pollutants elimination: In-operando generation of plasmonic Bi metal and oxygen vacancies.

Photocatalysis has been regarded as a sustainable strategy for wastewaters remediation, and sulfite addition could significantly accelerate the photocatalytic performances. However, the related mechanisms are still not well understood. Here, we for the first time found that plasmonic Bi and oxygen vacancies were in-operando generated on BiOX (X = Cl, Br, I) in the presence of sulfite under light irradiation. The oxidative degradation rate constants of 4-nitrophenol, bisphenol A, and phenol were improved by about 11.5, 4.7, and 12.2 times on BiOBr and 9.1, 1.6, and 3.1 times on BiOCl with addition of 5 mM sulfite, while the photocatalytic reduction rate of 4-nitrophenol to 4-aminophenol was promoted by approximate 31.7 times on BiOI. The results indicated that sulfite could improve the photooxidation ability of BiOBr and BiOCl and the photoreduction performance of BiOI, resulted from the improved light absorption and separation of photogenerated charge carriers. This work can provide exploratory platforms for understanding and maximizing the sulfite-assisted BiOX photocatalysis.

Surface-Enhanced Raman Spectroscopy Facilitates the Detection of Microplastics <1 µm in the Environment.

Micro- and nanoplastics are considered one of the top pollutants that threaten the environment, aquatic life, and mammalian (including human) health. Unfortunately, the development of uncomplicated but reliable analytical methods that are sensitive to individual microplastic particles, with sizes smaller than 1 µm, remains incomplete. Here, we demonstrate the detection and identification of (single) micro- and nanoplastics by using surface-enhanced Raman spectroscopy (SERS) with Klarite substrates. Klarite is an exceptional SERS substrate; it is shaped as a dense grid of inverted pyramidal cavities made of gold. Numerical simulations demonstrate that these cavities (or pits) strongly focus incident light into intense hotspots. We show that Klarite has the potential to facilitate the detection and identification of synthesized and atmospheric/aquatic microplastic (single) particles, with sizes down to 360 nm. We find enhancement factors of up to 2 orders of magnitude for polystyrene analytes. In addition, we detect and identify microplastics with sizes down to 450 nm on Klarite, with samples extracted from ambient, airborne particles. Moreover, we demonstrate Raman mapping as a fast detection technique for submicron microplastic particles. The results show that SERS with Klarite is a facile technique that has the potential to detect and systematically measure nanoplastics in the environment. This research is an important step toward detecting nanoscale plastic particles that may cause toxic effects to mammalian and aquatic life when present in high concentrations.

Optimizing nanocarbon shell in zero-valent iron nanoparticles for improved electron utilization in Cr(VI) reduction.

A core-shell structured zero-valent iron@carbon (ZVI@C) nanocompoiste was designed to improve the electron utilization of ZVI in the Cr(VI) reduction. The porosity of carbon layer in ZVI@C was optimized for improving the efficiency of electron utilization of ZVI in the Cr(VI) reduction process. The porous structure of carbon layer was controllably synthesized by adjusting the carbon source and the ratio of C/Fe in the precursor. The glucose was suggested as the optimal carbon source, and a high specific surface area (37.067 m2/g) was reached for the prepared ZVI@C when the ratio of C/Fe was controlled at 20. These ZVI@C performed well on Cr(VI) reduction, e.g. a complete reduction of Cr(VI) (2 mg/L) to Cr(III) within 10 min. The removal capacity (800 mg/g) exceeded previously recorded ZVI based adsorbents. The pH and initial Cr(VI) concentration were demonstrated as the key factors for the efficient electron utilization of ZVI. Furthermore, the efficiency of electron utilization of the ZVI increased up to 80% when the concentration of Cr(VI) was 2000 mg/L and the pH was controlled at 3, which was much higher than 8% of the naked ZVI.