RESUMO
On December 13, 2019, the Yale School of Public Health hosted a symposium titled "Per- and Polyfluoroalkyl Substances (PFAS): Challenges and Opportunities" in New Haven, Connecticut. The meeting focused on the current state of the science on these chemicals, highlighted the challenges unique to PFAS, and explored promising opportunities for addressing them. It brought together participants from Yale University, the National Institute of Environmental Health Sciences, the University of Massachusetts Amherst, the University of Connecticut, the Connecticut Agricultural Experiment Station, the Connecticut Departments of Public Health and Energy and Environmental Protection, and the public and private sectors. Presentations during the symposium centered around several primary themes. The first reviewed the current state of the science on the health effects associated with PFAS exposure and noted key areas that warranted future research. As research in this field relies on specialized laboratory analyses, the second theme considered commercially available methods for PFAS analysis as well as several emerging analytical approaches that support health studies and facilitate the investigation of a broader range of PFAS. Since mitigation of PFAS exposure requires prevention and cleanup of contamination, the third theme highlighted new nanotechnology-enabled PFAS remediation technologies and explored the potential of green chemistry to develop safer alternatives to PFAS. The fourth theme covered collaborative efforts to assess the vulnerability of in-state private wells and small public water supplies to PFAS contamination by adjacent landfills, and the fifth focused on strategies that promote successful community engagement. This symposium supported a unique interdisciplinary coalition established during the development of Connecticut's PFAS Action Plan, and discussions occurring throughout the symposium revealed opportunities for collaborations among Connecticut scientists, state and local officials, and community advocates. In doing so, it bolstered the State of Connecticut's efforts to implement the ambitious initiatives that its PFAS Action Plan recommends.
RESUMO
Upconversion (UC) of sub-bandgap photons extends the effective light absorption range of photovoltaic and photocatalytic devices, allowing them to reach higher conversion efficiencies. Recent advances in polymer host materials make it possible to translate triplet-triplet annihilation (TTA)-UC, the UC mechanism most suitable for this purpose, to solid films that can be integrated into devices. The promise of these films is currently limited by the narrow light absorption of TTA-UC sensitizer chromophores, but incorporating multiple sensitizers into layered film systems presents a promising strategy for producing UC materials with broadened light absorption. This strategy is herein applied for photocatalytic air purification, demonstrating its use in a real-world application for the first time. We superimpose optimized red-to-blue and green-to-blue UC films within dual-layer systems and develop a new photocatalyst compatible with their fluorescence emission. By integrating the dual-layer UC film systems with films of this photocatalyst, we produce the first devices that use TTA-UC to harness both red and green sub-bandgap photons for hydroxyl radical generation and photocatalytic degradation of gaseous acetaldehyde, a model volatile organic compound (VOC). Under white light-emitting diode excitation, the dual-layer film systems' broadened light absorption enhances their devices' photocatalytic degradation efficiency, enabling them to degrade twice as much acetaldehyde as their single-sensitizer counterparts. We show that as a result of the different absorption profiles of the two sensitizers, the film order significantly impacts UC fluorescence and VOC degradation. By probing the influence of the excitation light source, excitation geometry, and chromophore spectral overlap on the film systems' UC performance, we propose a framework for the design of multilayer TTA-UC film systems suitable for integration with a variety of photovoltaic and photocatalytic devices.
RESUMO
Triplet-triplet annihilation upconversion (TTA-UC) has recently drawn widespread interest for its capacity to harvest low-energy photons and to broaden the absorption spectra of photonic devices, such as solar cells. Although conceptually promising, effective integration of TTA-UC materials into practical devices has been difficult due to the diffusive and anoxic conditions required in TTA-UC host media. Of the solid-state host materials investigated, rubbery polymers facilitate the highest TTA-UC efficiency. To date, however, their need for long-term oxygen protection has limited rubbery polymers to rigid film architectures that forfeit their intrinsic flexibility. This study introduces a new multilayer thin-film architecture, in which scalable solution processing techniques are employed to fabricate flexible, photostable, and efficient TTA-UC thin films containing layers of oxygen barrier and host polymers. This breakthrough material design marks a crucial advance toward TTA-UC integration within rigid and flexible devices alike. Moreover, it introduces new opportunities in unexplored applications such as anticounterfeiting. Soft lithography is incorporated into the film fabrication process to pattern TTA-UC host layers with a broad range of high-resolution microscale designs, and superimposing host layers with customized absorption, emission, and patterning ultimately produces proof-of-concept anticounterfeiting labels with advanced excitation-dependent photoluminescent security features.
RESUMO
This study demonstrates the first reported photocatalytic decomposition of an indoor air pollutant, acetaldehyde, using low-energy, sub-bandgap photons harnessed through sensitized triplet-triplet annihilation (TTA) upconversion (UC). To utilize low-intensity noncoherent indoor light and maximize photocatalytic activity, we designed a plasmon-enhanced sub-bandgap photocatalyst device consisting of two main components: (1) TTA-UC rubbery polymer films containing broad-band plasmonic particles (Ag-SiO2) to upconvert sub-bandgap photons, and (2) nanodiamond (ND)-loaded WO3 as a visible-light photocatalyst composite. Effective decomposition of acetaldehyde was achieved using ND/WO3 (Eg = 2.8 eV) coupled with TTA-UC polymer films that emit blue photons (λEm = 425 nm, 2.92 eV) upconverted from green photons (λEx = 532 nm, 2.33 eV), which are wasted in most environmental photocatalysis. The overall photocatalytic efficiency was amplified by the broad-band surface plasmon resonance of AgNP-SiO2 particles incorporated into the TTA-UC films.
