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Abstract Activation of the dinitrogen triple bond is a crucial step in the overall fixation of atmospheric nitrogen into usable forms for industrial and biological applications. Current synthetic catalysts incorporate metal ions to facilitate the activation and cleavage of dinitrogen. The high price of metal‐based catalysts and the challenge of catalyst recovery during industrial catalytic processes has led to increasing interest in metal‐free catalysts. One step toward metal‐free catalysis is the use of frustrated Lewis pairs (FLPs). In this study, we have examined 18 functionalized carbenes as FLPs to elucidate the influence of steric and electronic effects on the activation of dinitrogen. To test the effects of functionalization on dinitrogen activation, we have performed density functional theory (DFT), multireference, non and extended transition state‐natural orbital for chemical valence (ETS‐NOCV) calculations. Our results suggest that functional groups which introduce strong electron‐withdrawing effects and/or engage in extended π/π* systems lead to the lowering of the dissociation energy of the dinitrogen bond, which further contributes to greater nitrogen activation. We conjecture that these effects are due to enhanced back‐bonding capability of the p orbital of the carbene carbon atoms to the adjacent nitrogen atoms (increasing Lewis basicity of the carbene carbon atom) and enhanced stability of dissociated products. Our concluding remarks include opportunities to extend this activation study to explore the entire catalytic cycle with promising functionalized carbenes for experimental evaluation.
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Raspberry Colloid Templated Catalysts Fabricated Using Spray Drying Method
The majority of industrial chemical processes—from production of organic and inorganic compounds to air and water treatment—rely on heterogeneous catalysts. The performance of these catalysts has improved over the past several decades; in parallel, many innovations have been presented in publications, demonstrating increasingly higher efficiency and selectivity. One common challenge to adopting novel materials in real-world applications is the need to develop robust and cost-effective synthetic procedures for their formation at scale. Herein, we focus on the scalable production of a promising new class of materials—raspberry-colloid-templated (RCT) catalysts—that have demonstrated exceptional thermal stability and high catalytic activity. The unique synthetic approach used for the fabrication of RCT catalysts enables great compositional flexibility, making these materials relevant to a wide range of applications. Through a series of studies, we identified stable formulations of RCT materials that can be utilized in the common industrial technique of spray drying. Using this approach, we demonstrate the production of highly porous Pt/Al2O3 microparticles with high catalytic activity toward complete oxidation of toluene as a model reaction.
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- Award ID(s):
- 2026128
- PAR ID:
- 10488824
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Catalysts
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 2073-4344
- Page Range / eLocation ID:
- 60
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/catal13010060
