Singlet oxygen (1O2) is a reactive oxygen species produced in sunlit waters via energy transfer from the triplet states of natural sensitizers. There has been an increasing interest in measuring apparent 1O2 quantum yields (ΦΔ) of aquatic and atmospheric organic matter samples, driven in part by the fact that this parameter can be used for environmental fate modeling of organic contaminants and to advance our understanding of dissolved organic matter photophysics. However, the lack of reproducibility across research groups and publications remains a challenge that significantly limits the usability of literature data. In the first part of this review, we critically evaluate the experimental techniques that have been used to determine ΦΔ values of natural organic matter, we identify and quantify sources of errors that potentially explain the large variability in the literature, and we provide general experimental recommendations for future studies. In the second part, we provide a qualitative overview of known ΦΔ trends as a function of organic matter type, isolation and extraction procedures, bulk water chemistry parameters, molecular and spectroscopic organic matter features, chemical treatments, wavelength, season, and location. This review is supplemented with a comprehensive database of ΦΔ values of environmental samples.

Triplet-state chromophoric dissolved organic matter (CDOM*) plays an important role in aquatic photochemistry, yet much remains unknown about the reactivity of these intermediates. To better understand the kinetic behavior and reactivity of CDOM*, we have developed an indirect observation method based on monitoring time-resolved singlet oxygen (O) phosphorescence kinetics. The underpinning principle of our approach relies on the fact that O quenches almost all triplets with near diffusion limited rate constants, resulting in the formation of O, which is kinetically linked to the precursors. A kinetic model relating O phosphorescence kinetics to triplet excited states produced from isolated humic substances and in whole natural-water samples (hereafter referred to as CDOM*) was developed and used to determine rate constants governingCDOM* natural lifetimes and quenching by oxygen and 2,4,6-trimethylphenol (TMP), a common triplet probe molecule. CDOM* was found to exhibit smaller O and TMP quenching rate constants, ∼9 × 10 and ∼8 × 10 M s, respectively, compared with model sensitizers, such as aromatic ketones. Findings from this report shed light on the fundamental photochemical properties of CDOM in organic matter isolates and whole waters and will help refine photochemical models to more accurately predict pollutant fate in the environment.

Singlet oxygen (1O2) generation quantum yields from chromophoric dissolved organic matter (CDOM) have been reported for many samples over the past 4 decades. Yet even for standardized isolates such as those from the International Humic Substance Society (IHSS), wide-ranging values exist in the literature. In this manuscript, time-resolved 1O2 phosphorescence was used to determine the 1O2 quantum yields (ΦΔ) of a variety of dissolved organic matter (DOM) isolates and natural waters. In general, the 1O2 quantum yield values in this study are in the middle, although below the median of the range of past reported values (e.g., for Suwannee River Natural Organic Matter IHSS isolate: 1.8% vs 0.23–2.89%). Notably, hydrophobic neutral fractions of DOM isolates were found to possess the highest 1O2 quantum yields, an interesting result given that these fractions are not retained in typical humic and fulvic acid isolation procedures that use XAD resins. The excitation wavelength dependence of 1O2 generation from CDOM was also examined, and an approximate linear decrease with longer excitation wavelength was observed. This work advances the understanding of CDOM photoprocesses, especially in relation to wavelength-dependent 1O2 production, which is valuable for assessing real-world environmental behavior.

Sorbic acid (2,4-hexadienoic acid; HDA) is commonly used as a probe and quencher for triplet-excited chromophoric dissolved organic matter (3CDOM*), an important transient species in natural waters, yet much remains unknown about its reactivity with 3CDOM* and its triplet energy. To better understand the quenching behavior of HDA, we measured HDA quenching rate constants for various humic substance isolates and whole waters with singlet oxygen (1O2) phosphorescence and determined the triplet energy of HDA. Low-temperature phosphorescence measurements determined the triplet energy of HDA to be 217 kJ mol–1, whereas a complementary method based on triplet quenching kinetics found a triplet energy of 184 ± 7 kJ mol–1. Time-resolved 1O2 phosphorescence measurements yielded different HDA quenching rate constants depending on the fitting method. Using an approach that considered the reactivity of the entire triplet pool produced values of (∼1–10) × 108 M–1 s–1, while an approach that considered only the reactivity of the high-energy triplets output higher rate constants ((∼7–30) × 108 M–1 s–1). In addition, the model based on high-energy triplet reactivity found that ∼30–60% of 3CDOM* is not quenched by HDA. Findings from this study provide a more comprehensive view on the use of HDA as a probe for 3CDOM*.

Solid supported fullerene materials are prepared in aims of creating a fullerene-based photocatalyst that is capable of producing (1)O2 in the aqueous phase. Past studies of using fullerene as a photocatalyst in water have exclusively focused on using water soluble fullerene derivatives and employed sophisticated chemistry to create immobilized fullerene materials. The method presented herein is much less synthetically complex and utilizes pristine fullerene, providing a drastically simpler route to supported fullerene materials and furthering their potential for use in environmental applications. Covalent immobilization was achieved through the nucleophilic addition of a terminal amine (located on a solid support) across a [6,6] fullerene double bond, resulting in attachment directly to C60's cage. Immobilization allowed supported fullerene moieties to produce (1)O2 in water under various illumination conditions and inactivate MS2 bacteriophages. In a water with natural organic matter, supported fullerene materials produced (1)O2 under visible light irradiation without exhibiting significant loss of photocatalytic activity after successive cycling.

We herein report the first instance of using pristine C70 as a heavy-atom free organic sensitizer for efficient triplet-triplet annihilation upconversion (UC) for both green-to-blue and red-to-green UC using 9,10-bis(phenylethynyl)anthracene and perylene as acceptors, respectively. C70 achieved quantum yields of 8% and 0.8% for green-to-blue and red-to-green UC, 25 to 35 times higher than C60, and showed improved stability under continuous laser irradiation compared to the benchmark platinum(II)-octaethylporphyrin.

We herein present the first instance of employing [C₇₀] fullerene for photocatalytic ¹O₂ production in water, through covalent immobilization onto a mesoporous silica support via nucelophilic amine addition directly to fullerene's cage. This attachment approach prevents the aggregation of individual fullerene molecules in water, thus allowing fullerene to retain its photoactivity, yet is much less complex than other techniques commonly pursued to create such supported-fullerene materials, which typically rely on water-soluble fullerene derivatives and elaborate immobilization methods. The solid-supported C₇₀ material exhibits significantly improved aqueous visible-light photoactivity compared to previous C₆₀- and C₆₀-derivative-based supported fullerene materials. Further, this material rapidly inactivates MS2 bacteriophage under sunlight illumination, oxidizes various organic contaminants, and does not appear to be significantly fouled by natural organic matter (NOM), highlighting the potential of these materials in real-world applications. Collectively, the ease of preparation and significantly enhanced visible-light photoactivity of these materials advance fullerene-based technologies for water treatment.

We present the facile prepartion of C and Ag nanoparticle (NP) loaded block copolymer (BCP) thin films, with C and Ag NPs working in tandem to provide virucidal and bactericidal activities, respectively. Polystyrene-block-poly-4-vinylpyridine (PS-P4VP) was used as a template, allowing C integration into PS domains and in situ formation of Ag NPs in P4VP domains, while providing control of the nanoscale spatial distribution of functionality as a function of BCP molecular weight (MW). C loaded PS-P4VP films were found to generate significant amounts of O under visible light illumination with no apparent dependence on BCP MW. An analogous C loaded PS homopolymer film produced notably less O, highlighting a possible critical role of morphology on C photoactivity. The antimicrobial activity of Ag NP and C loaded composites against the model PR772 bacteriophage and Escherichia coli was assessed, finding synergistic inactivation afforded by the dual functionality. BCPs were demonstrated as versatile platforms for the preparation of multifunctional antimicrobial coatings toward combating diverse microbial communities.