An official website of the United States government
Semiconductor Zn-based nanomaterials have emerged as promising agents for the photocatalytic degradation of organic pollutants in wastewater treatment. However, achieving efficient synthesis protocols capable of rapidly producing small structures directly in aqueous environments remains challenging. Microwave-assisted synthesis presents a viable solution by enabling one-step particle generation swiftly and directly in water through increased pressure, thereby easily elevating the boiling point. This study investigates the microwave-assisted one-step synthesis of pure and iron-doped ZnS nanoparticles and assesses their efficacy in photodegrading Quinoline Yellow (QY) in aqueous suspensions. The results demonstrate a significant degradation of QY in the presence of 1% iron-doped ZnS nanoparticles, achieving approximately 66.3% degradation with 500 ppm of doped nanoparticles after 270 min. These findings highlight the considerable potential of 1% iron-doped ZnS nanoparticles as effective nanocatalysts.
more »
« less
The Cost of Quantum Yield
The quantum yield (QY) of a photocatalytic reaction significantly influences its performance, as reactions with low QYs require more intense light sources and longer illumination times to achieve efficient reaction rates. Unfortunately, the importance of QY is often overlooked in the design of photocatalytic reactions for small-molecule synthesis, leading to potential cost implications and reduced productivity. This study examines various photochemical reactor designs from the literature to estimate photon flux and light generation costs and investigates the impact of QY on both cost and productivity. The findings reveal substantial penalties in cost and productivity when QYs are low. For instance, external QYs below 1% can result in significant light generation costs and maximum productivities of less than 1 mol of product per day. Moreover, the study highlights that high QYs have a larger effect on potential productivity than high product yields. By optimizing for QY instead of product yield, kinetic and revenue modeling for the photoredox-mediated synthesis of ceralasertib demonstrate the potential for generating hundreds of thousands of dollars in additional revenue per day. Overall, this work emphasizes the need for increased consideration of QY in the design of photocatalytic reactions.
more »
« less
- Award ID(s):
- 2047492
- PAR ID:
- 10430898
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Organic Process Research & Development
- Volume:
- 27
- Issue:
- 7
- ISSN:
- 1083-6160
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Visible‐light‐driven C−C bond formation utilizing ketyl radical (Cketyl) species has attracted increasing attention recently, as it provides a direct route for the synthesis of complex molecules. However, the most‐developed homogeneous photocatalytic systems for the generation and utilization of ketyl radicals usually entail noble metal‐based (e. g., Ru and Ir) photosensitizers, which suffer from not only high cost but also potential degradation and hence pose challenges in product separation and purification. In contrast, readily accessible, inexpensive, and recyclable semiconductors represent a class of attractive and alternative photocatalysts but remain much less explored for photocatalytic ketyl radical initiated C−C bond formation. This work demonstrates that a wide range of industrially important chemicals, including substituted chromanes and tertiary alcohols, can be produced on ZnIn2S4under visible light irradiation through intramolecular cyclization (Cketyl−Csp2) and intermolecular cross‐coupling (Cketyl−Csp3) reactions, respectively, using ketyl radicals. A suite of experimental studies aided by computational investigation were carried out to shed light on the mechanistic insights of these two types of ketyl radical initiated C−C coupling reactions on ZnIn2S4.more » « less
-
Abstract Hydrogen gas is a prominent focus in pursuing renewable and clean alternative energy sources. The quest for maximizing hydrogen production yield involves the exploration of an ideal photocatalyst and the development of a simple, cost‐effective technique for its generation. Iron titanate has garnered attention in this context due to its photocatalytic properties, affordability, and non‐toxic nature. Over the years, different synthesis routes, different morphologies, and some modifications of iron titanate have been carried out to improve its photocatalytic performance by enhancing light absorption in the visible region, boosting charge carrier transfer, and decreasing recombination of electrons and holes. The use of iron titanate photocatalyst for hydrogen evolution reaction has seen an upward trend in recent times, and based on available findings, more can be done to improve the performance. This review paper provides a comprehensive overview of the fundamental principles of photocatalysis for hydrogen generation, encompassing the synthesis, morphology, and application of iron titanate‐based photocatalysts. The discussion delves into the limitations of current methodologies and present and future perspectives for advancing iron titanate photocatalysts. By addressing these limitations and contemplating future directions, the aim is to enhance the properties of materials fabricated for photocatalytic water splitting.more » « less
-
CuBiW 2 O 8 (CBTO), with a band gap of 1.9–2.0 eV, responds to a wide region of the electromagnetic spectrum, which makes it a good candidate for solar-driven photocatalytic energy conversion and water treatment. We have previously demonstrated a Cu-rich solid state approach that enables the synthesis of CBTO accompanied by thermodynamically stable Bi 2 WO 6 impurity. Here, we describe an improved synthesis protocol with decreased impurity and synthesis time, and the first demonstration of CBTO as a functional material using photocatalytic Cr( vi ) photoreduction as a probe reaction. Transient absorption spectroscopy (TAS) was performed to investigate the ultrafast dynamics of the charge carriers after photoexcitation. The presence of two populations of photoexcited carriers was found, including short-lived free carriers with ∼10 ps lifetime and long-lived shallowly-trapped carriers with ∼1 ns lifetime. Together with carrier mobilities measured in our previous study, the new TAS results indicate that the long-lived charges have diffusion lengths similar to the CBTO particle size and were likely responsible for the majority of the photocatalytic activity. High activity of CBTO for Cr( vi ) photoreduction (∼100% reduction of 5 mg L −1 of Cr( vi ) in 15 minutes) was demonstrated, which clearly establishes the promise of this novel oxide for visible light-driven photocatalytic applications. Radical quenching experiments indicate that both ˙OH radicals and O 2 ˙ − radicals are produced by CBTO and are involved in the photoreduction of Cr( vi ). Repeated photocatalysis tests and analysis of the surface after the reaction show that CBTO is a stable and potentially reusable catalyst. Insights gained from correlating the synthesis conditions, carrier dynamics, and reactive species suggests that CBTO prepared with the improved protocol would be a favorable choice for photocatalytic reactions such as water decontamination from organic pollutants, water splitting, and solar fuel generation using visible light.more » « less
-
null (Ed.)Due to its clean and sustainable nature, solar energy has been widely recognized as a green energy source in driving a variety of reactions, ranging from small molecule activation and organic transformation to biomass valorization. Within this context, organic reactions coupled with H 2 evolution via semiconductor-based photocatalytic systems under visible light irradiation have gained increasing attention in recent years, which utilize both excited electrons and holes generated on semiconductors and produce two types of value-added products, organics and H 2 , simultaneously. Based on the nature of the organic reactions, in this review article we classify semiconductor-based photocatalytic organic transformations and H 2 evolution into three categories: (i) photocatalytic organic oxidation reactions coupled with H 2 production, including oxidative upgrading of alcohols and biomass-derived intermediate compounds; (ii) photocatalytic oxidative coupling reactions integrated with H 2 generation, such as C–C, C–N, and S–S coupling reactions; and (iii) photo-reforming reactions together with H 2 formation using organic plastics, pollutants, and biomass as the substrates. Representative heterogeneous photocatalytic systems will be highlighted. Specific emphasis will be placed on their synthesis, characterization, and photocatalytic mechanism, as well as the organic reaction scope and practical application.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.oprd.3c00167
