skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: 100% selective cyclotrimerization of acetylene to benzene on Ag(111)
If a critical acetylene surface coverage threshold above one monolayer is attained, acetylene conversion to benzene occurs with 100% selectivity on Ag(111). The presence of multiple monolayers has the unforeseen effect of increasing benzene production while maintaining selectivity.  more » « less
Award ID(s):
2154952
PAR ID:
10586807
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
Royal Society of Chemistry
Date Published:
Journal Name:
Chemical Science
Volume:
15
Issue:
18
ISSN:
2041-6520
Page Range / eLocation ID:
6716 to 6725
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract The Cu(II)‐mediated Chan‐Lam coupling reaction offers several benefits for developing point‐of‐care detection devices on microelectrode arrays. However, achieving selectivity on borate ester‐based polymer surfaces has proven difficult due to background reactions. Fluorescence‐based studies were conducted using fluorescently labeled acetylene nucleophiles. Initial experiments revealed significant background fluorescence across the electrode array, indicating selectivity issues. Further investigation uncovered significant background reactions occurring even without copper. To address this, a strategy utilizing an arylbromide‐based polymer was developed, enhancing reaction selectivity by minimizing background non‐specific reactions. Exploration into the confinement mechanism revealed the role of acetylene in forming dimers, facilitating rapid consumption of Cu(II) reagents that escaped from the specific electrodes used. These findings offer a way to construct devices for the multiplex point‐of‐care detection of metabolites, improving performance and accuracy in diagnostic devices. 
    more » « less
  2. Titan’s equatorial dunes represent the most monumental surface structures in our Solar System, but the chemical composition of their dark organics remains a fundamental, unsolved enigma, with solid acetylene detected near the dunes implicated as a key feedstock. Here, we reveal in laboratory simulation experiments that aromatics such as benzene, naphthalene, and phenanthrene—prospective building blocks of the organic dune material—can be efficiently synthesized via galactic cosmic ray exposure of low-temperature acetylene ices on Titan’s surface, hence challenging conventional wisdom that aromatic hydrocarbons are formed solely in Titan’s atmosphere. These processes are also of critical importance in unraveling the origin and chemical composition of the dark surfaces of airless bodies in the outer Solar System, where hydrocarbon precipitation from the atmosphere cannot occur. This finding notably advances our understanding of the distribution of carbon throughout our Solar System such as on Kuiper belt objects like Makemake. 
    more » « less
  3. A direct, catalytic conversion of benzene to phenol would have wide-reaching economic impacts. Fe zeolites exhibit a remarkable combination of high activity and selectivity in this conversion, leading to their past implementation at the pilot plant level. There were, however, issues related to catalyst deactivation for this process. Mechanistic insight could resolve these issues, and also provide a blueprint for achieving high performance in selective oxidation catalysis. Recently, we demonstrated that the active site of selective hydrocarbon oxidation in Fe zeolites, named α-O, is an unusually reactive Fe(IV)=O species. Here, we apply advanced spectroscopic techniques to determine that the reaction of this Fe(IV)=O intermediate with benzene in fact regenerates the reduced Fe(II) active site, enabling catalytic turnover. At the same time, a small fraction of Fe(III)-phenolate poisoned active sites form, defining a mechanism for catalyst deactivation. Density-functional theory calculations provide further insight into the experimentally defined mechanism. The extreme reactivity of α-O significantly tunes down (eliminates) the rate-limiting barrier for aromatic hydroxylation, leading to a diffusion-limited reaction coordinate. This favors hydroxylation of the rapidly diffusing benzene substrate over the slowly diffusing (but more reactive) oxygenated product, thereby enhancing selectivity. This defines a mechanism to simultaneously attain high activity (conversion) and selectivity, enabling the efficient oxidative upgrading of inert hydrocarbon substrates. 
    more » « less
  4. Abstract There has been significant interest in developing new catalytic systems to convert linear chain alkanes into olefins and aromatics. In the case of higher alkanes (≥C6), the production of aromatic compounds such as benzene‐toluene‐xylenes is highly desirable. However, as the length of the carbon chain increases, the dehydrogenation process becomes more complex, not only due to the challenges of C−H activation but also the need for selectivity towards the desired products by the possibility of side reactions such as isomerization and cracking. Here, we present a detailed analysis of the dehydroaromatization of n‐hexane, n‐heptane, and n‐octane, using PtSn intermetallic nanoparticles supported on SBA‐15 as the catalyst. Throughin situspectroscopic and kinetic analysis, we have probed the reaction kinetics and catalyst deactivation, and provided a mechanistic understanding of the dehydroaromatization process on the surface of the PtSn intermetallic nanoparticles. Introducing Sn has been shown to be crucial not only for enhancement of catalytic activity, but also for higher aromatics selectivity and stability on stream. Furthermore, the analysis of dehydroaromatization reaction rates of reactant and possible intermediates indicates that the dehydroaromatization of n‐hexane to benzene likely proceeds through initial dehydrogenation steps followed by ring closing. 
    more » « less
  5. The catalytic activity and selectivity of two different water-soluble palladium nanoparticles capped with 5-(trimethylammonio)pentanethiolate and 6-(carboxylate)hexanethiolate ligands are investigated using the catalytic reaction of allyl benzene. The results show that the regioselective transformation of allyl benzene to 3-phenylpropanal occurs at room temperature and under atmospheric pressure in neat water via a Tsuji–Wacker type oxidation. Conventionally, the Tsuji–Wacker oxidation promotes the Markovnikov oxidation of terminal alkenes to their respective ketones in the presence of dioxygen. Water-soluble Pd nanoparticles, however, catalyze the anti-Markovnikov oxidation of allyl benzene to 3-phenylpropanal in up to 83% yields. Catalytic results of other aromatic alkenes suggest that the presence of benzylic hydrogen is a key to the formation of a p-allyl Pd intermediate and the anti-Markovnikov addition of H2O. The subsequent b-H elimination and tautomerization contribute to the formation of aldehyde products. Water-soluble Pd nanoparticles are characterized using nuclear magnetic resonance (NMR), UV–vis spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). Catalysis results are examined using 1H NMR and/or GC-MS analyses of isolated reaction mixtures. 
    more » « less