The conformal nanoporous inorganic coatings with accessible pores that are stable under applied thermal and mechanical stresses represent an important class of materials used in the design of sensors, optical coatings, and biomedical systems. Here, we synthesize porous AlOx and ZnO coatings by the sequential infiltration synthesis (SIS) of two types of polymers that enable the design of porous conformal coatings—polymers of intrinsic microporosity (PIM) and block co-polymer (BCP) templates. Using quartz crystal microbalance (QCM), we show that alumina precursors infiltrate both polymer templates four times more efficiently than zinc oxide precursors. Using the quartz crystal microbalance (QCM) technique, we provide a comprehensive study on the room temperature accessibility to water and ethanol of pores in block copolymers (BCPs) and porous polymer templates using polystyrene-block-poly-4-vinyl pyridine (PS75-b-P4VP25) and polymers of intrinsic microporosity (PIM-1), polymer templates modified by swelling, and porous inorganic coatings such as AlOx and ZnO synthesized by SIS using such templates. Importantly, we demonstrate that no structural damage occurs in inorganic nanoporous AlOx and ZnO coatings synthesized via infiltration of the polymer templates during the water freezing/melting cycling tests, suggesting excellent mechanical stability of the coatings, even though the hardness of the inorganic nanoporous coating is affected by the polymer and precursor selections. We show that the hardness of the coatings is further improved by their annealing at 900 °C for 1 h, though for all the cases except ZnO obtained using the BCP template, this annealing has a negligible effect on the porosity of the material, as is confirmed by the consistency in the optical characteristics. These findings unravel new potential for the materials being used across various environment and temperature conditions.
This content will become publicly available on February 1, 2025
Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.
more » « less- Award ID(s):
- 2045662
- NSF-PAR ID:
- 10487173
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Polymers
- Volume:
- 16
- Issue:
- 3
- ISSN:
- 2073-4360
- Page Range / eLocation ID:
- 308
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Cinzia Casiragi (Ed.)Melanin is a stable, widely light-absorbing, photoactive, and biocompatible material viable for energy con- version, photocatalysis, and bioelectronic applications. To achieve multifunctional nanostructures, we synthesized melanin nanoparticles of uniform size and controlled chemical composition (dopamelanin and eumelanin) and used them with titanium dioxide to fabricate donor–acceptor bilayers. Their size enhances the surface-to-volume ratio important for any surface-mediated functionality, such as photo- catalysis, sensing, and drug loading and release, while controlling their chemical composition enables to control the film’s functionality and reproducibility. Inkjet printing uniquely allowed us to control the de- posited amount of materials with minimum ink waste suitable for reproducible materials deposition. We studied the photochemical characteristics of the donor–acceptor melanin–TiO2 nanostructured films via photocatalytic degradation of methylene blue dye under selective UV-NIR and Vis-NIR irradiation con- ditions. Under both irradiation conditions, they exhibited photocatalytic characteristics superior to pure melanin and, under UV-NIR irradiation, superior to TiO2 alone; TiO2 is photoactive only under UV irradiation. The enhanced photocatalytic characteristics of the melanin–TiO2 nanostructured bilayer films, particularly when excited by visible light, point to charge separation at the melanin–TiO2 interface as a possible mechanism. We performed ultrafast laser spectroscopy to investigate the photochemical charac- teristics of pure melanin and the melanin–TiO2 constructs and found that their time-resolved photo- excited spectral patterns differ. We performed singular value decomposition analysis to quantitatively deconvolute and compare the dynamics of photochemical processes for melanin and melanin–TiO2 heterostructures. This observation supports electronic interactions, namely, interfacial charge separation at the melanin and TiO2 interface. The excited-state relaxation in melanin–TiO2 increases markedly from 5 ps to 400 ps. The results are remarkable for the future intriguing application of melanin-based con- structs for bioelectronics and energy conversion.more » « less
-
Photocatalysis, mainly using TiO2 as a catalyst, has emerged as a promising method to address the issue of wastewater treatment. This study explores the enhanced photocatalytic activity of TiO2 through the introduction of reduced graphene oxide (rGO) and cadmium sulfide (CdS) as selective metal dopants. The incorporation of rGO and CdS into the TiO2 lattice aims to optimize its photocatalytic properties, including bandgap engineering, charge carrier separation, and surface reactivity. The unique combination of CdS and rGO with TiO2 is expected to boost degradation efficiency and reduce the reliance on expensive and potentially harmful sensitizers. This experimental investigation involves the synthesis and characterization of TiO2-based photocatalysts. The photocatalytic degradation of methyl orange (MO) and methylene blue (MB) was assessed under controlled laboratory conditions, studying the influence of metal dopants on degradation kinetics and degradation efficiency. Furthermore, the synthesized photocatalyst is characterized by advanced techniques, including BET, SEM, TEM, XRD, and XPS analyses. The degraded samples were analyzed by UV-Vis spectroscopy. Insights into the photoexcitation and charge transfer processes shed light on the role of metal dopants in enhancing photocatalytic performance. The results demonstrate the potential of a TiO2-rGO-CdS-based photocatalyst in which 100% degradation was achieved within four hours for MO and six hours for MB, confirming efficient azo dye degradation. The findings contribute to understanding the fundamental principles underlying the photocatalytic process and provide valuable guidance for designing and optimizing advanced photocatalytic systems. Ultimately, this research contributes to the development of sustainable and effective technologies for removing azo dyes from various wastewaters, promoting environmental preservation and human well-being.
-
null (Ed.)We report a photo-triggered, base generating, base propagating degradable polyurethane that is triggered by 365 nm UV light irradiation. A small area of this polyurethane material can be exposed to 365 nm UV light irradiation to generate basic species that can initiate a base propagated degradation process within the bulk material leading to global degradation without the need for continous UV irradiation. The polymer was synthesized by a polycondensation polymerization of a small amount of o -nitrobenzene diol 2 , a large amount of Fmoc-based diol 3 , and hexylmethylene diisocyanate. Integrating both photosensitive and base-sensitive carbamate moieties into the polymer 1 backbone provides the UV light-triggered base propagating degradable polyurethane material. Degradation studies of polymer 1 using 1 H NMR and gel permeation chromatography (GPC) suggest that initial UV irradiation triggers the degradation of the photosensitive o -nitrobenzene carbamate linkages, releasing a primary amino group that causes a cascade of amines to form by further degrading the remaining Fmoc carbamate groups. A bulk polyurethane film was prepared using Fmoc-based triol 4 as a monomer. UV-irradiation of a small localized area of the film initiates the propagation throughout, leading to efficient bulk degradation of the entire material. The amine degradation products could be utilized to make a one-pot epoxy adhesive, showing a potential upcycling application of this self-propagating degradable polyurethane system.more » « less
-
Abstract A mesoporous TiO2−
x material comprised of small, crystalline, vacancy‐rich anatase nanoparticles (NPs) shows unique optical, thermal, and electronic properties. It is synthesized using polymer‐derived mesoporous carbon (PDMC) as a template. The PDMC pores serve as physical barriers during the condensation and pyrolysis of a titania precursor, preventing the titania NPs from growing beyond 10 nm in size. Unlike most titania nanomaterials, during pyrolysis the NPs undergo no transition from the anatase to rutile phase and they become catalytically active reduced TiO2−x . When exposed to a slow electron beam, the NPs exhibit a charge/discharge behavior, lighting up and fading away for an average period of 15 s for an extended period of time. The NPs also show a 50 nm red‐shift in their UV/Vis absorption and long‐lived charge carriers (electrons and holes) at room temperature in the dark, even long after UV irradiation. The NPs as photocatalysts show a good activity for CO2reduction.