Molecular orientation of molybdate ions adsorbed on goethite nanoparticles revealed by polarized in situ ATR-IR spectroscopy

Davantès, A.; Lefèvre, Grégory

doi:10.1016/j.susc.2016.06.007

Cited by 11 publications

(20 citation statements)

References 21 publications

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“…The adsorption of octahedrally coordinated decavanadate species on ferrihydrite and hematite surfaces is likely constrained to monodentate surface complexes due to its large and rigid structure. Similarly, the adsorption of VO 2 + at pH 3 and [V] T below 250 μM is limited to outer-sphere and inner-sphere monodentate adsorption. , Attenuation of polynuclear V(V) species is inhibited onto less crystalline Fe (oxyhydr)oxide surfaces (e.g., ferrihydrite, lepidocrocite, and goethite) at moderate pH conditions, which is consistent with previous studies on Mo and W polynuclear species. ,, The observed stability of aqueous V polynuclear species over a wide pH range (2–9) may have implications for V mobility within soils and sediments. Overall, these results demonstrate that (poly)vanadate species form surface polymers on ferrihydrite and hematite surfaces.…”

Section: Discussionsupporting

confidence: 89%

“…This hypothesis is supported by a higher number of bands attributed to the complexation of polymeric species with hematite surfaces (Figure ) and to the higher affinity of (poly)vanadates for hematite based on Langmuir isotherms (Figure and Table S3). Preferential polymer formation at the hexagonal (0001) hematite crystal face compared to that at less crystalline Fe(III) (oxyhydr)oxides has previously been demonstrated for polynuclear Mo and W sorption. ,, Unlike polymolybdate, epitaxial growth of decavanadate on hematite is likely inhibited by its large structure . However, previous studies have observed the substitution of metavanadate and decavanadate species into layered-double hydroxides. − At concentrations below 250 μM, the oxycation VO 2 + represents more than 60% of [V] T at pH 3 (Figure ).…”

Section: Discussionmentioning

confidence: 94%

“…Preferential polymer formation at the hexagonal (0001) hematite crystal face compared to that at less crystalline Fe(III) (oxyhydr)oxides has previously been demonstrated for polynuclear Mo and W sorption. 34,38,68 Unlike polymolybdate, epitaxial growth of decavanadate on hematite is likely inhibited by its large structure. 38 However, previous studies have observed the substitution of metavanadate and decavanadate species into layered-double hydroxides.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…26,66 Attenuation of polynuclear V(V) species is inhibited onto less crystalline Fe (oxyhydr)oxide surfaces (e.g., ferrihydrite, lepidocrocite, and goethite) at moderate pH conditions, which is consistent with previous studies on Mo and W polynuclear species. 34,38,68 The observed stability of aqueous V polynuclear species over a wide pH range (2−9) may have implications for V mobility within soils and sediments. Overall, these results demonstrate that (poly)vanadate species form surface polymers on ferrihydrite and hematite surfaces.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

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Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Study

Vessey

Schmidt

Abdolahnezhad

et al. 2020

ACS Earth Space Chem.

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Vanadium (V) geochemistry offers insight into Earth’s global biogeochemical cycles over geologic time. Additionally, increasing anthropogenic release of this redox-sensitive metal has led to elevated V concentrations in soils, sediments, and waters. Although Fe (oxyhydr)oxides are important sinks for aqueous V in soils and sediments, our understanding of adsorption mechanisms is currently limited to mononuclear species (i.e., H x VO4 (3–x)–). Here, we use in situ attenuated total reflectance–Fourier transform infrared spectroscopy to examine the sorption mechanisms for (poly)vanadate attenuation by ferrihydrite and hematite from pH 3 to 6. Adsorption isotherms illustrate the low affinity of polyvanadate species for ferrihydrite surfaces compared to that for hematite. Mononuclear V species (i.e., [H x VO4](3–x)– and VO2 +) were present at all experimental conditions. At low surface loadings and pH values of 5 and 6, H2VO4 – adsorption onto ferrihydrite and hematite surfaces results in the formation of inner-sphere complexes. At [V]T above 250 μM, adsorbed polynuclear V species in this study include H2V2O7 2– and V4O12 4–, whereas, HV10O28 6–, H3V10O28 5–, and NaHV10O28 4– are the predominant adsorbed species at pH values of 3 and 4 and elevated [V]T’s. Surface polymers were identified on hematite at all experimental pH values, whereas polymeric adsorption onto ferrihydrite was limited to pH values of 3 and 4. Results also suggest that hematite is a more suitable substrate for polymer complexation than ferrihydrite. Our results demonstrate the pH- and concentration-dependent removal of (poly)vanadate species by Fe(III) (oxyhydr)oxides, which has implications for understanding V mobility, behavior, and fate in the environment.

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Section: Discussionsupporting

confidence: 89%

Section: Discussionmentioning

confidence: 94%

Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: ■ Materials and Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Study

Vessey

Schmidt

Abdolahnezhad

et al. 2020

ACS Earth Space Chem.

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“…In addition, it was proposed that Mo(VI) is adsorbed on the (010) surface of lepidocrocite (γ-FeOOH) by forming monodentate mononuclear complexes using density functional theory (DFT) calculations and in situ Fourier transform infrared (FTIR). 18,19 In general, the current understanding of the local structure of Mo(VI) adsorbed on the surface of goethite remains controversial and deep discussion at the molecular level is still lacking.…”

Section: ■ Introductionmentioning

confidence: 99%

Molecular Structure of Molybdate Adsorption on Goethite at pH 5–8: A Combined DFT + U, EXAFS, and Ab Initio XANES Study

et al. 2021

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The adsorption of molybdate on goethite plays an important role in its reactivity, speciation, mobility, and bioavailability. However, the current understanding of the molybdate adsorption mechanism on the surface of goethite remains controversial. In this contribution, samples of molybdate-adsorbed goethite have been synthesized at various pH values (5−8) and a pH value of 7 with varying Fe/Mo molar ratios (10− 100). All molybdate-adsorbed samples have similar X-ray absorption near-edge spectroscopy (XANES) features and have a pre-edge feature that lies in the middle between reference compounds containing tetrahedral MoO 4 (pH 7 Mo(VI) solution, Na 2 MoO 4 •2H 2 O, and Fe 2 (MoO 4 ) 3 ) and distorted octahedral MoO 6 (pH 4 Mo(VI) solution and MoO 3 ) groups, suggesting the formation of fivefold coordinated molybdate oxyanions on the surface of goethite. This suggestion is further supported by combined density functional theory (DFT) + U calculations and ab initio XANES analyses, which also demonstrate that the corner-sharing monodentate mononuclear complex between molybdate oxyanions and goethite surfaces is energetically more stable than the corner-sharing bidentate binuclear complexation on the surface of goethite. These results shed new light on the mechanistic understanding of molybdate adsorption on goethite and define the nature of the bonding environment of adsorbed molybdate in this mineral structure.

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A deep look into the diverse surface speciation of the mono-molybdate/lepidocrocite system by ATR-IR and polarized ATR-IR spectroscopy

Botella

Lefèvre

2022

Colloids and Surfaces A: Physicochemical and Engineering Aspect

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Molecular orientation of molybdate ions adsorbed on goethite nanoparticles revealed by polarized in situ ATR-IR spectroscopy

Cited by 11 publications

References 21 publications

Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Study

Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Study

Molecular Structure of Molybdate Adsorption on Goethite at pH 5–8: A Combined DFT + U, EXAFS, and Ab Initio XANES Study

A deep look into the diverse surface speciation of the mono-molybdate/lepidocrocite system by ATR-IR and polarized ATR-IR spectroscopy

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