An official website of the United States government
Abstract Photocatalysis is an attractive, energy-efficient technology for organic transformations, polymer synthesis, and degradation of environmental pollutants. There is a need for new photocatalysts stable in different media and that can be tailored for specific applications. Covalent organic frameworks (COF) are crystalline, nanoporous materials withπ-conjugated backbone monomers, representing versatile platforms as heterogeneous, metal-free photocatalysts. The backbone structure can be tailored to achieve desired photocatalytic properties, side-chains can mediate adsorption, and the nanoporous structure provides large surface area for molecular adsorption. While these properties make COFs attractive as photocatalysts, several fundamental questions remain regarding mechanisms for different photocatalytic transformations, reactant transport into porous COF structures, and both structural and chemical stability in various environments. In this perspective, we provide a brief overview of COF photocatalysts and identify challenges that should be addressed in future research seeking to employ COFs as photocatalysts. We close with an outlook and perspective on future research directions in the area of COF photocatalysts.
more »
« less
Photocatalytic Activity: Experimental Features to Report in Heterogeneous Photocatalysis
Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic light. In this regard, an astonishing number of recent research articles include claims of highly efficient (photo)catalysts or similar terms about materials with superior or enhanced efficiency for a given reaction without proper experimental support. Consequently, the comparison of the efficiencies of photocatalysts may result as being meaningless, especially when reports are only based on expressions determining (1) a reaction rate per weight of catalyst or its surface area, (2) quantum efficiencies or quantum yields, and (3) turnover frequencies or turnover numbers. Herein, we summarize the standards needed for reporting valuable data in photocatalysis and highlight some common discrepancies found in the literature. This work should inform researchers interested in reporting photocatalysis projects about the correct procedures for collecting experimental data and properly characterizing the materials by providing examples and key supporting literature.
more »
« less
- Award ID(s):
- 1255290
- PAR ID:
- 10107212
- Date Published:
- Journal Name:
- Materials
- Volume:
- 11
- Issue:
- 10
- ISSN:
- 1996-1944
- Page Range / eLocation ID:
- 1990
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Plasmonic photocatalysis is an emerging research field that holds promise for sustainable energy applications, particularly in solar energy conversion. In this study, we focus on the enhancement of broadband light absorption capabilities for plasmonic photocatalyst under white light illumination. By replacing parts of the catalyst with solar absorber, we can significantly improve the total reaction rate under mild heating conditions with less catalyst. Through careful comparison of reaction conditions and systematic optimization of the contributions from photothermal and non-thermal effects, we demonstrate a substantial enhancement in broadband light absorption capacity and overall light effectiveness, paving the way for advanced plasmonic photocatalysts with greater efficiency and practical applicability using solar light as the energy source.more » « less
-
Abstract The manipulation of carbon nitride (CN) structures is one main avenue to enhance the activity of CN‐based photocatalysts. Increasing the efficiency of photocatalytic heterogeneous materials is a critical step toward the realistic implementation of sustainable schemes for organic synthesis. However, limited knowledge of the structure/activity relationship in relation to subtle structural variations prevents a fully rational design of new photocatalytic materials, limiting practical applications. Here, the CN structure is engineered by means of a microwave treatment, and the structure of the material is shaped around its suitable functionality for Ni dual photocatalysis, with a resulting boosting of the reaction efficiency toward many CX (X = N, S, O) couplings. The combination of advanced characterization techniques and first‐principle simulations reveals that this enhanced reactivity is due to the formation of carbon vacancies that evolve into triazole and imine N species able to suitably bind Ni complexes and harness highly efficient dual catalysis. The cost‐effective microwave treatment proposed here appears as a versatile and sustainable approach to the design of CN‐based photocatalysts for a wide range of industrially relevant organic synthetic reactions.more » « less
-
Abstract In its 60 years of existence, the field of nonlinear optics has gained momentum especially over the past two decades thanks to major breakthroughs in material science and technology. In this article, we present a new set of data tables listing nonlinear-optical properties for different material categories as reported in the literature since 2000. The papers included in the data tables are representative experimental works on bulk materials, solvents, 0D–1D–2D materials, metamaterials, fiber waveguiding materials, on-chip waveguiding materials, hybrid waveguiding systems, and materials suitable for nonlinear optics at THz frequencies. In addition to the data tables, we also provide best practices for performing and reporting nonlinear-optical experiments. These best practices underpin the selection process that was used for including papers in the tables. While the tables indeed show strong advancements in the field over the past two decades, we encourage the nonlinear-optics community to implement the identified best practices in future works. This will allow a more adequate comparison, interpretation and use of the published parameters, and as such further stimulate the overall progress in nonlinear-optical science and applications.more » « less
-
null (Ed.)The production of hydrogen fuels, via water splitting, is of practical relevance for meeting global energy needs and mitigating the environmental consequences of fossil-fuel-based transportation. Water photoelectrolysis has been proposed as a viable approach for generating hydrogen, provided that stable and inexpensive photocatalysts with conversion efficiencies over 10% can be discovered, synthesized at scale, and successfully deployed (Pinaud et al. , Energy Environ. Sci. , 2013, 6 , 1983). While a number of first-principles studies have focused on the data-driven discovery of photocatalysts, in the absence of systematic experimental validation, the success rate of these predictions may be limited. We address this problem by developing a screening procedure with co-validation between experiment and theory to expedite the synthesis, characterization, and testing of the computationally predicted, most desirable materials. Starting with 70 150 compounds in the Materials Project database, the proposed protocol yielded 71 candidate photocatalysts, 11 of which were synthesized as single-phase materials. Experiments confirmed hydrogen generation and favorable band alignment for 6 of the 11 compounds, with the most promising ones belonging to the families of alkali and alkaline-earth indates and orthoplumbates. This study shows the accuracy of a nonempirical, Hubbard-corrected density-functional theory method to predict band gaps and band offsets at a fraction of the computational cost of hybrid functionals, and outlines an effective strategy to identify photocatalysts for solar hydrogen generation.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/ma11101990
