Photocatalysis of chloroform degradation by μ-dichlorotetrachlorodipalladate(II)

Gilbert, Rachel M.; Karabulut, Merve; Hoggard, Patrick E.

doi:10.1016/j.ica.2010.01.032

Cited by 11 publications

(7 citation statements)

References 43 publications

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“…Much of the recent work in our laboratory has been on the catalyzed decomposition of chloroalkanes (29)(30)(31)(32)(33)(34)(35)(36); thus, we have followed with special interest the published work on the photodecomposition of chloroalkanes and chloroarenes by modified mesoporous silica (27,(37)(38)(39)(40)(41)(42)(43)(44). These studies have incorporated a wide variety of modifications.…”

Section: Introductionmentioning

confidence: 99%

Photodecomposition of Chloroform Catalyzed by Unmodified MCM‐41 Mesoporous Silica

Peña

Chan

Cohen

et al. 2014

Photochem & Photobiology

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Unactivated MCM-41 mesoporous silica catalyzes the photodecomposition of chloroform to phosgene and hydrogen chloride under near-UV (λ > 360 nm) irradiation. The rate of photodecomposition increases toward an asymptotic limit as the O(2) partial pressure is increased. Deuterochloroform does not decompose under the same experimental conditions. Low concentrations of both cyclohexane and ethanol quench the photodecomposition, whereas water, up to its solubility limit, does not. Dissolved tetraalkylammonium salts suppress photodecomposition. The data are consistent with a mechanism in which light absorption by an SiO(2) defect yields an electron-deficient oxygen atom, which then abstracts hydrogen from chloroform. The resulting CCl(3) radicals react with oxygen to form a peroxy radical that decomposes, eventually yielding phosgene and hydrogen chloride.

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Section: Introductionmentioning

confidence: 99%

Photodecomposition of Chloroform Catalyzed by Unmodified MCM‐41 Mesoporous Silica

Peña

Chan

Cohen

et al. 2014

Photochem & Photobiology

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“…While these and other mechanisms lead to photocatalyzed decomposition, the situation is often complicated by a transformation of the original chlorometallate complex to another species under irradiation , which can greatly obscure mechanistic conclusions.…”

Section: Introductionmentioning

confidence: 99%

“…A complex that does appear to catalyze chloroform decomposition in this way is [Ru(bpy) 2 Cl 2 ] + , which, when excited, apparently oxidizes ClÀ to Cl (17). *Corresponding author email: phoggard@scu.edu (Patrick E. Hoggard) While these and other (1,4) mechanisms lead to photocatalyzed decomposition, the situation is often complicated by a transformation of the original chlorometallate complex to another species under irradiation (2)(3)(4)18), which can greatly obscure mechanistic conclusions.…”

Section: Introductionmentioning

confidence: 99%

“…Several chlorometallate complexes have been found to catalyze the photodecomposition of liquid chloroform , effectively raising the threshold wavelength for decomposition from ca 260 nm for neat chloroform, in some cases to well above 400 nm . Although the mechanism of catalysis appears to vary among the chlorometallate complexes, most of the mechanisms have in common the production of a radical, leading to the sequence of steps shown below.…”

Section: Introductionmentioning

confidence: 99%

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Photocatalysis of Chloroform Decomposition by the Hexachlororuthenate(IV) Ion

Chan

Peña

Segura

et al. 2012

Photochem & Photobiology

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Dissolved hexachlororuthenate(IV) effectively catalyzes the photodecomposition of chloroform to hydrogen chloride and phosgene under near-UV (λ > 345 nm) irradiation, whereby RuCl6(2-) is not itself photocatalytically active, but is photochemically transformed into a species that is active, possibly RuCl5 (CHCl3 )(-) . Conversion to a photoactive species during irradiation is consistent with the acceleration of the decomposition rate during the early stages and with the apparent inverse dependence of the decomposition rate on the initial concentration of RuCl6(2-) . The displacement of Cl(-) by CHCl3 in the coordination sphere to create the photoactive species is consistent with the retardation of photodecomposition by both Cl(-) and H2 O. The much smaller photodecomposition rate in CDCl3 suggests that C-H bond dissociation occurs during the primary photochemical event, which is also consistent with the presence of a CHCl3 molecule in the first coordination sphere.

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“…Neat chloroform can be photodecomposed by the catalytic effect of several chlorometallate complexes under UV irradiation . Even though the mechanism of catalysis is still debated, to the best of our knowledge, chloroform molecules are, in fact, photodissociated to form HCl and CCl 3 radicals. , Subsequently, Zn(II) ions are trapped by chloride, and successive reactions of H + with pyridyl ligand give rise to quaternary ammonium salt-type HL + . Such a reaction condition under UV irradiation, in other words, stabilizes the crystals in chloroform media, where solubilized species then react with the dissociated H + , I 3 – , and I 2 .…”

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confidence: 99%

Host–Guest Conversion: Transformation of Diiodomethane within 1D-Ensemble Suprachannels into Triiodide–Iodine Channel via Photoreaction

Lee

Hwang

Naveen

et al. 2018

Crystal Growth & Design

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Self-assembly of ZnBr 2 with 2,7-bis(isonicotinoyloxy)naphthalene (L) yields one-dimensional (1D) zigzag chains of [ZnBr 2 L] composition. This 1D chain ensemble forms unique suprachannels of 4.0 × 4.2 Å 2 size via weak C−H•••π and π•••π interactions. A 350 nm ultraviolet irradiation affects host−guest conversion. Diiodomethane molecules within the suprachannel structure of CHCl 3 • CH 2 I 2 @[ZnBr 2 L] were transformed into an unprecedented triiodide−iodine channel skeleton, HL + @[I 3 •I 2 ] − . Specifically, two clear, quasi-reversible redox peaks were observed at +0.33 and +0.70 V versus Ag/AgCl in the anodic scan and at +0.19 and +0.62 V in the cathodic scan in acetonitrile for HL + @[I 3 •I 2 ] − .

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Photocatalysis of chloroform degradation by μ-dichlorotetrachlorodipalladate(II)

Cited by 11 publications

References 43 publications

Photodecomposition of Chloroform Catalyzed by Unmodified MCM‐41 Mesoporous Silica

Photodecomposition of Chloroform Catalyzed by Unmodified MCM‐41 Mesoporous Silica

Photocatalysis of Chloroform Decomposition by the Hexachlororuthenate(IV) Ion

Host–Guest Conversion: Transformation of Diiodomethane within 1D-Ensemble Suprachannels into Triiodide–Iodine Channel via Photoreaction

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