Water Vapor Condensation Triggers Simultaneous Oxidation and Hydrolysis of Organic Pollutants on Iron Mineral Surfaces.

Increasing worldwide contamination with organic chemical compounds is a paramount environmental challenge facing humanity. Once they enter nature, pollutants undergo transformative processes that critically shape their environmental impacts and associated risks. This research unveils previously overlooked yet widespread pathways for the transformations of organic pollutants triggered by water vapor condensation, leading to spontaneous oxidation and hydrolysis of organic pollutants. These transformations exhibit variability through either sequential or parallel hydrolysis and oxidation, contingent upon the functional groups within the organic pollutants. For instance, acetylsalicylic acid on the goethite surface underwent sequential hydrolysis and oxidation that first hydrolyzed to salicylic acid followed by hydroxylation oxidation of the benzene moiety driven by the hydroxyl radical (•OH). In contrast, chloramphenicol underwent parallel oxidation and hydrolysis, forming hydroxylated chloramphenicol and 2-amino-1-(4-nitrophenyl)-1,3-propanediol, respectively. The spontaneous oxidation and hydrolysis occurred consistently on three naturally abundant iron minerals with the key factors being •OH production capacity and surface binding strength. Given the widespread presence of iron minerals on Earth's surface, these spontaneous transformation paths could play a role in the fate and risks of organic pollutants of health concerns.

Spontaneous Oxidation of Thiols and Thioether at the Air-Water Interface of a Sea Spray Microdroplet.

The transport of dissolved organic sulfur, including thiols and thioethers, from the ocean surface to the atmosphere through sea spray aerosol (SSA) is of great importance for the global sulfur cycle. Thiol/thioether in SSA undergoes rapid oxidation that is historically linked to photochemical processes. Here, we report the discovery of a non-photochemical, spontaneous path of thiol/thioether oxidation in SSA. Among 10 investigated naturally abundant thiol/thioether, seven species displayed rapid oxidation in SSA, with disulfide, sulfoxide, and sulfone comprising the major products. We suggest that such spontaneous oxidation of thiol/thioether was mainly fueled by thiol/thioether enrichment at the air-water interface and generation of highly reactive radicals by the loss of an electron from ions (e.g., glutathionyl radical produced from ionization of deprotonated glutathione) at or near the surface of the water microdroplet. Our work sheds light on a ubiquitous but previously overlooked pathway of thiol/thioether oxidation, which could contribute to an accelerated sulfur cycle as well as related metal transformation (e.g., mercury) at ocean-atmosphere interfaces.

Accelerated Photolysis of H2O2 at the Air-Water Interface of a Microdroplet.

Photochemical homolysis of hydrogen peroxide (H2O2) occurs widely in nature and is a key source of hydroxyl radicals (·OH). The kinetics of H2O2 photolysis play a pivotal role in determining the efficiency of ·OH production, which is currently mainly investigated in bulk systems. Here, we report considerably accelerated H2O2 photolysis at the air-water interface of microdroplets, with a rate 1.9 × 103 times faster than that in bulk water. Our simulations show that due to the trans quasiplanar conformational preference of H2O2 at the air-water interface compared to the bulk or gas phase, the absorption peak in the spectrum of H2O2 is significantly redshifted by 45 nm, corresponding to greater absorbance of photons in the sunlight spectrum and faster photolysis of H2O2. This discovery has great potential to solve current problems associated with ·OH-centered heterogeneous photochemical processes in aerosols. For instance, we show that accelerated H2O2 photolysis in microdroplets could lead to markedly enhanced oxidation of SO2 and volatile organic compounds.

Water Vapor Condensation on Iron Minerals Spontaneously Produces Hydroxyl Radical.

The hydroxyl radical (•OH) is a potent oxidant and key reactive species in mediating element cycles and pollutant dynamics in the natural environment. The natural source of •OH is historically linked to photochemical processes (e.g., photoactivation of natural organic matter or iron minerals) or redox chemical processes (e.g., reaction of microbe-excreted or reduced iron/natural organic matter/sulfide-released electrons with O2 in soils and sediments). This study revealed a ubiquitous source of •OH production via water vapor condensation on iron mineral surfaces. Distinct •OH productions (15-478 nM via water vapor condensation) were observed on all investigated iron minerals of abundant natural occurrence (i.e., goethite, hematite, and magnetite). The spontaneous •OH productions were triggered by contact electrification and Fenton-like activation of hydrogen peroxide (H2O2) at the water-iron mineral interface. Those •OH drove efficient transformation of organic pollutants associated on iron mineral surfaces. After 240 cycles of water vapor condensation and evaporation, bisphenol A and carbamazepine degraded by 25%-100% and 16%-51%, respectively, forming •OH-mediated arene/alkene hydroxylation products. Our findings largely broaden the natural source of •OH. Given the ubiquitous existence of iron minerals on Earth's surface, those newly discovered •OH could play a role in the transformation of pollutants and organic carbon associated with iron mineral surfaces.

Rare-earth single atoms decorated 2D-TiO2 nanosheets for the photodegradation of gaseous O-xylene.

In this work, rare-earth single atoms (La, Er) were decorated on the surface of 2D-TiO2 nanosheets by an impregnation-calcination strategy. The formation of rare-earth single atoms was certified by AC HAADF-STEM and XAS. TiO2 decorated with rare-earth single atoms (La1-TiO2 and Er1-TiO2) exhibited outstanding photocatalytic activity than pure 2D-TiO2 nanosheets (2D-TiO2) towards gas-phase degradation of O-xylene. Compared with 2D-TiO2, the rare-earth single atoms greatly improved the adsorption capacity of O-xylene without increasing their specific surface area. This is because rare-earth single atoms provide additional adsorption sites and reduce the adsorption energy of O-xylene. In addition, the hybrid orbital formed by the combination of rare-earth single atom and oxygen atom is beneficial to the rapid transmission and separation of photo-induced electrons, thereby improving the performance of photocatalytic degradation. In addition, in-situ DRIFTS and GC-MS were used to reveal the photocatalytic oxidation mechanism. Interestingly, the results showed that the La1-TiO2 and Er1-TiO2 samples can reduce the types of intermediates and simplify the reaction route, implying that the single atoms play an important role in the modulation and thorough mineralization of intermediate products. This work shows that the rare-earth single atom decorated 2D-TiO2 nanosheets have great potential in photocatalytic air pollution control.

Improved photocatalytic oxidation performance of gaseous acetaldehyde by ternary g-C3N4/Ag-TiO2 composites under visible light.

In the process of photocatalytic oxidation (PCO), titanium dioxide (TiO2) shows excellent capabilities. However, when TiO2 is used to remove volatile organic compounds (VOCs), there are some drawbacks including weak adsorption of gaseous contaminants, insufficient utilization of sunlight, and rapid recombination of photogenerated carriers. Herein, a TiO2-based ternary heterogeneous photocatalyst, g-C3N4/Ag-TiO2, was successfully fabricated to photodegrade gaseous acetaldehyde (one of the representatives of oxygenated VOCs) under visible light. Among the various samples, the g-C3N4/50 wt% Ag-TiO2 exhibited an excellent photocatalytic activity, which was 5.8 times of bare TiO2. The mineralization efficiency of acetaldehyde was also increased by 3.7 times compared to bare TiO2. The substantial improvement in the PCO performance of the ternary system can be associated with the good adsorption to acetaldehyde gas and light-harvesting capability, as well as improved charge separation process. The application of Langmuir-Hinshelwood kinetic model suggested that relative humidity played a significant role in the VOCs degradation. Also, the photodegradation of gaseous acetaldehyde primarily occurred on the catalysts surface. Based on several characterizations, i.e., UV-vis spectroscopy, photoluminescence spectrum, photocurrent spectroscopy and electron spin-resonance test, a suitable degradation mechanism is proposed. This study provides a novel ternary photocatalyst with improved photocatalytic performance and stability, which can be used for the low-concentration VOCs abatement in the indoor environment.

Carbon quantum dots-TiO2 nanocomposite as an efficient photocatalyst for the photodegradation of aromatic ring-containing mixed VOCs: An experimental and DFT studies of adsorption and electronic structure of the interface.

In this work, we have developed and optimized TiO2 nanoparticles decorated with carbon quantum dots to examine its potential use in the photocatalytic oxidation of aromatic ring containing gas-phase mixed volatile organic compounds, e.g., benzene, toluene, and p-xylene. Carbon quantum dots decorated TiO2 demonstrated good photodegradation efficiency in contrast to pure TiO2 under UV-vis light illumination. For example, with 0.5 wt% carbon quantum dots decorated on TiO2, 64 % of the mixed volatile organic compounds were photodegraded, while pure TiO2 only exhibited 44 % of the photodegradation efficiency. Also, the carbon quantum dots (0.5 wt%)/TiO2 nanocomposite demonstrated considerable photocatalytic activity within the visible region. On the other hand, pure TiO2 remained inactive within the visible region. The density functional theory study of the carbon quantum dots/TiO2 interface revealed that C 2p states of carbon quantum dots incorporated new energy states around the Fermi level near the lowest conduction band. This might be accountable for the improved charge separation process and better conductivity of the photogenerated electrons. The improved photocatalytic performance of the carbon quantum dots/TiO2 nanocomposites can be attributed to good light harvesting within the UV-vis region, charge separation, and adsorption capability.