The interaction of water with organophosphonic acid surface modified titania: An in-depth in-situ DRIFT study

Dijck, Jeroen G. Van; Lenaerts, Hilde; Siemons, Laurens; Blockhuys, Frank; Meynen, Vera

doi:10.1016/j.surfin.2020.100710

Cited by 7 publications

(7 citation statements)

References 38 publications

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“…This methodology was previously validated and documented in the existing literature. 63,64 The analysis of the TGA-profile considered the mass loss between 423 K and 1073 K, assuming that toluene, used as a solvent and rinsing agent in the post-synthesis modification protocol, had evaporated below this temperature.…”

Section: Experimental Methodsmentioning

confidence: 99%

Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H₂ clathrate hydrate

Kummamuru,

Ciocarlan,

Houlleberghs

et al. 2024

Sustainable Energy Fuels

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Section: Experimental Methodsmentioning

confidence: 99%

Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H₂ clathrate hydrate

Kummamuru,

Ciocarlan,

Houlleberghs

et al. 2024

Sustainable Energy Fuels

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“…After digestion, 16 mL of H 3 BO 3 (4%) was added to neutralize the HF. The modification degree in number of grafted groups per nm 2 (#groups/nm 2 ) was calculated from the weight percentage of phosphorus according to eq , mod nobreak0em.25em⁡ . .25em normald normale normalg normalr . ( # n m 2 ) = normalw normalt .25em % ( P ) × N normalA normalM normalM ( P ) × S normalB normalE normalT × 100 in which wt % (P) is the weight percentage of phosphorus in the sample, MM (P) is the molar mass of phosphorus (g/mol), S BET (nm 2 /g) is the surface area of the unmodified TiO 2 powder, and N A is Avogadro’s constant (molecules/mol). The experimental error is estimated to be 0.1 groups/nm 2 based on four repeated modifications under fixed synthesis conditions.…”

Section: Methodsmentioning

confidence: 99%

Amino-Alkylphosphonate-Grafted TiO₂: How the Alkyl Chain Length Impacts the Surface Properties and the Adsorption Efficiency for Pd

Gys

Pawlak

et al. 2022

ACS Omega

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Amino-alkylphosphonic acid-grafted TiO2 materials are of increasing interest in a variety of applications such as metal sorption, heterogeneous catalysis, CO2 capture, and enzyme immobilization. To date, systematic insights into the synthesis–properties–performance correlation are missing for such materials, albeit giving important know-how towards their applicability and limitations. In this work, the impact of the chain length and modification conditions (concentration and temperature) of amino-alkylphosphonic acid-grafted TiO2 on the surface properties and adsorption performance of palladium is studied. Via grafting with aminomethyl-, 3-aminopropyl-, and 6-aminohexylphosphonic acid, combined with the spectroscopic techniques (DRIFT, 31P NMR, XPS) and zeta potential measurements, differences in surface properties between the C1, C3, and C6 chains are revealed. The modification degree decreases with increasing chain length under the same synthesis conditions, indicative of folded grafted groups that sterically shield an increasing area of binding sites with increasing chain length. Next, all techniques confirm the different surface interactions of a C1 chain compared to a C3 or C6 chain. This is in line with palladium adsorption experiments, where only for a C1 chain, the adsorption efficiency is affected by the precursor concentration used for modification. The absence of a straightforward correlation between the number of free NH2 groups and the adsorption capacity for the different chain lengths indicates that other chain-length-specific surface interactions are controlling the adsorption performance. The increasing pH stability in the order of C1 < C3 < C6 can possibly be associated to a higher fraction of inaccessible hydrophilic sites due to the presence of folded structures. Lastly, the comparison of adsorption performance and pH stability with 3-aminopropyl(triethoxysilane)-grafted TiO2 reveals the applicability of both grafting methods depending on the envisaged pH during sorption.

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“…The rate of change in descending order was 3APPA20 > 3PPA20 > 3PPA150 > 3APPA150. Since the presence and adsorption of water at the surface plays a role in the ageing, differences in surface coverage of grafted groups influenced the number of surface adsorption sites for water, [32] and thus could be responsible for the difference in the susceptibility towards ageing. For example, modification degrees of 0.6 and 0.8 groups/nm 2 were obtained for 3APPA20 and 3APPA150, respectively.…”

Section: Chempluschemmentioning

confidence: 99%

“…An explanation for this relatively high photocatalytic activity could thus be found in studies evaluating the interaction between water and organophosphonic acid modified TiO 2 surface at the molecular level. Recently, Van Dijck et al [32] studied the water desorption behaviour of propyl-and phenylphosphonic acid P25 via an in-depth IR study at different hydration degrees to reveal the nature and strength of interaction between water and the modified surface. Their results showed that polymeric water chains interact more weakly on a modified surface compared to native P25, which was in line with the decrease in However, the signals related to molecularly adsorbed water and surface hydroxyl groups on the modified surfaces persisted upon progressive heating, while these signals already disappeared for P25 at the same conditions.…”

Section: Underlying Properties and Mechanism Governing Degradationmentioning

confidence: 99%

Self‐Induced and Progressive Photo‐Oxidation of Organophosphonic Acid Grafted Titanium Dioxide

et al. 2023

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While synthesis‐properties‐performance correlations are being studied for organophosphonic acid grafted TiO2, their stability and the impact of the exposure conditions on possible changes in the interfacial surface chemistry remain unexplored. Here, the impact of different ageing conditions on the evolution of the surface properties of propyl‐ and 3‐aminopropylphosphonic acid grafted mesoporous TiO2 over a period of 2 years is reported, using solid‐state 31P and 13C NMR, ToF‐SIMS and EPR as main techniques. In humid conditions under ambient light exposure, PA grafted TiO2 surfaces initiate and facilitate photo‐induced oxidative reactions, resulting in the formation of phosphate species and degradation of the grafted organic group with a loss of carbon content ranging from 40 to 60 wt %. By revealing its mechanism, solutions were provided to prevent degradation. This work provides valuable insights for the broad community in choosing optimal exposure/storage conditions that extend the lifetime and improve the materials′ performance, positively impacting sustainability.

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The interaction of water with organophosphonic acid surface modified titania: An in-depth in-situ DRIFT study

Cited by 7 publications

References 38 publications

Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H₂ clathrate hydrate

Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H₂ clathrate hydrate

Amino-Alkylphosphonate-Grafted TiO₂: How the Alkyl Chain Length Impacts the Surface Properties and the Adsorption Efficiency for Pd

Self‐Induced and Progressive Photo‐Oxidation of Organophosphonic Acid Grafted Titanium Dioxide

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The interaction of water with organophosphonic acid surface modified titania: An in-depth in-situ DRIFT study

Cited by 7 publications

References 38 publications

Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H2 clathrate hydrate

Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H2 clathrate hydrate

Amino-Alkylphosphonate-Grafted TiO2: How the Alkyl Chain Length Impacts the Surface Properties and the Adsorption Efficiency for Pd

Self‐Induced and Progressive Photo‐Oxidation of Organophosphonic Acid Grafted Titanium Dioxide

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Product

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Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H₂ clathrate hydrate

Surface modification of mesostructured cellular foam to enhance hydrogen storage in binary THF/H₂ clathrate hydrate

Amino-Alkylphosphonate-Grafted TiO₂: How the Alkyl Chain Length Impacts the Surface Properties and the Adsorption Efficiency for Pd