Chemiresistive metal-stabilized thiyl radical films as highly selective ethylene sensors

Chauhan, Rajat; Moreno, Mónica Cárdenas; Banda, Douglas M.; Grapperhaus, Craig A.

doi:10.1039/c4ra07560a

Cited by 16 publications

(16 citation statements)

References 21 publications

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“…All solvents were purified using an MBraun solvent purification system prior to use. The catalyst ReL 3 and the catalyst precursor [ReL 3 ][PF 6 ] were prepared according to previously reported literature methods.…”

Section: Experimental Sectionmentioning

confidence: 99%

Translation of Ligand-Centered Hydrogen Evolution Reaction Activity and Mechanism of a Rhenium-Thiolate from Solution to Modified Electrodes: A Combined Experimental and Density Functional Theory Study

et al. 2017

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The homogeneous, nonaqueous catalytic activity of the rhenium-thiolate complex ReL (L = diphenylphosphinobenzenethiolate) for the hydrogen evolution reaction (HER) has been transferred from nonaqueous homogeneous to aqueous heterogeneous conditions by immobilization on a glassy carbon electrode surface. A series of modified electrodes based on ReL and its oxidized precursor [ReL][PF] were fabricated by drop-cast methods, yielding catalytically active species with HER overpotentials for a current density of 10 mA/cm, ranging from 357 to 919 mV. The overpotential correlates with film resistance as measured by electrochemical impedance spectroscopy and film morphology as determined by scanning and transmission electron microscopy. The lowest overpotential was for films based on the ionic [ReL][PF] precursor with the inclusion of carbon black. Stability measurements indicate a 2 to 3 h conditioning period in which the overpotential increases, after which no change in activity is observed within 24 h or upon reimmersion in fresh aqueous, acidic solution. Electronic spectroscopy results are consistent with ReL as the active species on the electrode surface; however, the presence of an undetected quantity of catalytically active degradation species cannot be excluded. The HER mechanism was evaluated by Tafel slope analysis, which is consistent with a novel Volmer-Heyrovsky-Tafel-like mechanism that parallels the proposed homogeneous HER pathway. Proposed mechanisms involving traditional metal-hydride processes vs ligand-centered reactivity were examined by density functional theory, including identification and characterization of relevant transition states. The ligand-centered path is energetically favored with protonation of cis-sulfur sites culminating in homolytic S-H bond cleavage with H evolution via H atom coupling.

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Section: Experimental Sectionmentioning

confidence: 99%

Translation of Ligand-Centered Hydrogen Evolution Reaction Activity and Mechanism of a Rhenium-Thiolate from Solution to Modified Electrodes: A Combined Experimental and Density Functional Theory Study

et al. 2017

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“…The second step involves the formation of the S−C bond by attack of the Cu‐stabilized S‐centered incipient thiyl radical in 3 to alkyne 2 c . Whereas attack of a free S‐centered radical to an alkyne is a well‐documented process, the reactivity of a metal‐stabilized thiyl radical with an unsaturated fragment is much less common …”

Section: Resultsmentioning

confidence: 99%

“…The second step involves the formation of the SÀCb ond by attack of the Cu-stabilized S-centered incipientt hiyl radical in 3 to alkyne 2c.W hereas attack of af ree S-centered radical to an alkyne is aw ell-documentedp rocess, [82,83] the reactivity of a metal-stabilized thiyl radicalw ith an unsaturated fragment is much less common. [84][85][86][87] Species 3·alkyne is the van der Waals complex formed between 3 and the alkyne (the shortest CuÀC alkyne and SÀC alkyne distances are 3.20 and 4.0 ,r espectively). This intermediate is taken as the origin of energy in the S-and O-addition to alkyner eactions (Figures 5a nd 6).…”

Section: Secondstep:c àScouplingmentioning

confidence: 99%

Selective Synthesis of Tetrasubstituted Olefins by Copper‐Mediated Acetoxythiolation of Internal Alkynes: Scope and Mechanistic Studies

Villuendas

Ruiz

Vidossich

et al. 2018

Chemistry A European J

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The Cu-mediated synthesis of tetrasubstituted olefins by the addition of an acetate group and a thiolate to an unactivated internal alkyne is described. The reaction is fully stereoselective, because only the E alkene is obtained. If the alkyne is asymmetric, the reaction also shows a very high degree of regioselectivity. The mechanism of the reaction is elucidated by DFT methods, which show that it takes place through Cu-stabilized radical species. Calculations highlight the crucial role of the dimeric copper(II) diacetate in the process, as it generates the active species in which the sulfur center has an incipient thiyl radical character and accepting, through a series of changes in the oxidation states of the two copper centers, the two electrons released in the addition of two nucleophiles to the alkyne.

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“…Ethylene sensors based on chemoresistive [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18], optical (NDIR) [19][20][21][22], colorimetric [23][24][25], luminescence [26], fluorescence [27], piezoelectric [28][29][30], and electrochemical [31][32][33][34] principles have been developed. Each such principle has its own advantages and limitations, the comparison of which can be found in several review articles [35][36][37][38].…”

Section: Introductionmentioning

confidence: 99%

An Electrochemical Amperometric Ethylene Sensor with Solid Polymer Electrolyte Based on Ionic Liquid

Kuberský

Navrátil

Syrový

et al. 2021

Sensors

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An electrochemical amperometric ethylene sensor with solid polymer electrolyte (SPE) and semi-planar three electrode topology involving a working, pseudoreference, and counter electrode is presented. The polymer electrolyte is based on the ionic liquid 1-butyl 3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][NTf2] immobilized in a poly(vinylidene fluoride) matrix. An innovative aerosol-jet printing technique was used to deposit the gold working electrode (WE) on the solid polymer electrolyte layer to make a unique electrochemical active SPE/WE interface. The analyte, gaseous ethylene, was detected by oxidation at 800 mV vs. the platinum pseudoreference electrode. The sensor parameters such as sensitivity, response/recovery time, repeatability, hysteresis, and limits of detection and quantification were determined and their relation to the morphology and microstructure of the SPE/WE interface examined. The use of additive printing techniques for sensor preparation demonstrates the potential of polymer electrolytes with respect to the mass production of printed electrochemical gas sensors.

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Chemiresistive metal-stabilized thiyl radical films as highly selective ethylene sensors

Abstract: A highly selective chemiresistive ethylene sensor based on reversible and selective ligand-centered substrate binding to a metal-stabilized thiyl radical.

Cited by 16 publications

References 21 publications

Translation of Ligand-Centered Hydrogen Evolution Reaction Activity and Mechanism of a Rhenium-Thiolate from Solution to Modified Electrodes: A Combined Experimental and Density Functional Theory Study

Translation of Ligand-Centered Hydrogen Evolution Reaction Activity and Mechanism of a Rhenium-Thiolate from Solution to Modified Electrodes: A Combined Experimental and Density Functional Theory Study

Selective Synthesis of Tetrasubstituted Olefins by Copper‐Mediated Acetoxythiolation of Internal Alkynes: Scope and Mechanistic Studies

An Electrochemical Amperometric Ethylene Sensor with Solid Polymer Electrolyte Based on Ionic Liquid

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