The binding of phosphonic acids at aluminium oxide surfaces and correlation with passivation of aluminium flake

Cooper, Rachel J.; Camp, Philip J.; Henderson, David K.; Lovatt, Paul A.; Nation, David A.; Richards, S. Raymond; Tasker, Peter A.

doi:10.1039/b617599f

Cited by 7 publications

(7 citation statements)

References 46 publications

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“…Carboxylate linkages to TiO 2 are labile in organic solvents, as evidenced by the evolution of mixed monolayers from kinetically controlled to thermodynamically controlled compositions. Phosphonic acids adsorb more strongly than carboxylic acids to metal oxides. − To investigate the influence of the surface-attachment interaction on the formation and compositional evolution of mixed monolayers, we prepared mixed monolayers of MHDA and HPA (Chart ). Monolayers were prepared from coadsorption solutions in THF with χ T ,soln of 0.1, 0.5, and 0.9.…”

Section: Resultsmentioning

confidence: 99%

“…Phosphonic acids adsorb more strongly than carboxylic acids to metal oxides. [87][88][89] To investigate the influence of the surface-attachment interaction on the formation and compositional evolution of mixed monolayers, we prepared mixed monolayers of MHDA and HPA (Chart 1). Monolayers were prepared from coadsorption solutions in THF with χ T,soln of 0.1, 0.5, and 0.9.…”

Section: Resultsmentioning

confidence: 99%

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Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO₂

et al. 2009

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Mixed monolayers of thiol-terminated (T) and methyl-terminated (Me) carboxylic acids on nanocrystalline TiO(2) films underwent dimerization-induced compositional changes. At short reaction times, the compositions of mixed monolayers were kinetically controlled and mirrored the compositions of coadsorption solutions. On time scales up to several hours, well after the establishment of saturation surface coverages, the monolayers relaxed to thermodynamically controlled compositions through the displacement of Me by T. Equilibration was driven by the formation of intermolecular disulfide bonds between thiol groups of adsorbed T, which yielded polydentate dimeric adsorbates that were bound more strongly than monomeric adsorbates to TiO(2). The rate of compositional changes increased with decreasing solvent viscosity and decreasing alkyl chain length of T, suggesting that the rate of adsorption of T to TiO(2) strongly influenced the overall kinetics under certain conditions. Steric bulk within adsorbates and the strength of surface-attachment interactions also influenced the rate of compositional changes. A kinetic model, derived on the basis of Langmuir adsorption and desorption kinetics, accounts for key aspects of the mixed-monolayer compositional changes. The rate-determining step in the overall mechanism involved either the adsorption of T or the formation of disulfide bonds, depending on the conditions under which monolayers were prepared. Our findings illustrate that dimerization and other intermolecular interactions between adsorbates may dramatically influence the composition and terminal functionalization of mixed monolayers.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO₂

et al. 2009

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“…Supporting Information is available: experimental methods associated with ligand exchange reactivity, attempted syntheses, a determination of maximum nanoparticle surface coverage and solubility studies; a table for comparing key stretching bands observed by FTIR spectroscopy; a table of important 13 C NMR and FTIR data for literature diacyl disulfides; and experimental spectra. Additional referenced cited within the Supporting Information [50–59] …”

Section: Supporting Informationmentioning

confidence: 99%

Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide

Cowie

Häfele

Phanopoulos

et al. 2023

Chemistry A European J

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This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo‐copper precursor, mesitylcopper(I) [CuMes]z (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu2O or Cu2S nanoparticles. Use of sub‐stoichiometric quantities of protonated ligand (pro‐ligand; 0.1–0.2 equivalents vs. [CuMes]z) allows saturation of surface coordination sites but avoids excess pro‐ligand contaminating the nanoparticle solutions. The pro‐ligands are nonanoic acid (HO2CR1), 2‐[2‐(2‐methoxyethoxy)ethoxy]acetic acid (HO2CR2) or di(thio)nonanoic acid, (HS2CR1), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu2O is preferentially coordinated by carboxylate ligands and Cu2S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well‐defined nanoparticles and the need for appropriate ligand selection.

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“…This behavior distinguishes them from the corresponding aminocarboxylates, which exhibit much weaker interactions with mineral surfaces, especially near neutral pH. Some of the investigated adsorbents for phosphonates are calcite, clays, aluminum oxides, iron oxides, zinc oxide, hydroxoapatite, and barite. − For all those compounds very strong adsorption is observed in the pH range of natural waters. On the other hand, in the case of the presence of metal ions such as Fe(III), Zn(II), or Cu(II), strong adsorption of the uncomplexed phosphonates, which resulted in a dissociation of the complexes on metal ions and the phosphonates, was discovered.…”

Section: Introductionmentioning

confidence: 99%

Cu(II), Zn(II), Ni(II), and Cd(II) Complexes with HEDP Removal from Industrial Effluents on Different Ion Exchangers

Kołodyńska

2010

Ind. Eng. Chem. Res.

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The aim of this research is to investigate sorption characteristic of polyacrylate anion exchangers and chelating ion exchangers for the removal of Cu(II), Zn(II), Ni(II), and Cd(II) complexes with HEDP (1-hydroxyethylene-1,1-diphosphonic acid) from aqueous solutions. Optimum sorption conditions were determined as a function of phase contact time (1−180 min), pH (5−13), ion exchanger dosage (0.1−1.0 g), temperature (293−333 K), and chloride ions concentration (0.01−0.5 mol/L of NaCl). The Langmuir, Freundlich, Temkin, and Dubinin−Radushkevich (D−R) models were applied to describe the adsorption isotherm of Cu(II), Zn(II), Ni(II), and Cd(II) complexes with HEDP on Amberlite IRA 458 and Amberlite IRA 958 as well as Purolite S-920 and Purolite S-930. In the case of M(II)−HEDP complexes the adsorption capacities of Amberlite 458 were found to be 1.96 meq/g for Cu(II), 3.94 meq/g for Zn(II), 2.98 meq/g for Ni(II), and 4.25 meq/g for Cd(II). The metal ions were desorbed using 1 M HCl. The ion exchange capacity of ion exchangers applied decreased 8% in the recovery of Cu(II)−HEDP after 10 times of the sorption−desorption processess. Experimental data were also tested in terms of sorption kinetics using the pseudo-first-order and pseudo-second-order kinetic models. The results showed that the sorption processes of Cu(II), Zn(II), Ni(II), and Cd(II) complexes with HEDP on Amberlite IRA 458 and Amberlite IRA 958 as well as Purolite S-920 and Purolite S-930 followed well the pseudo-second-order kinetics.

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The binding of phosphonic acids at aluminium oxide surfaces and correlation with passivation of aluminium flake

Cited by 7 publications

References 46 publications

Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO₂

Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO₂

Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide

Cu(II), Zn(II), Ni(II), and Cd(II) Complexes with HEDP Removal from Industrial Effluents on Different Ion Exchangers

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The binding of phosphonic acids at aluminium oxide surfaces and correlation with passivation of aluminium flake

Cited by 7 publications

References 46 publications

Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO2

Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO2

Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide

Cu(II), Zn(II), Ni(II), and Cd(II) Complexes with HEDP Removal from Industrial Effluents on Different Ion Exchangers

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Product

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Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO₂

Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO₂