Surfactant-assisted synthesis of titanium nanoMOFs for thin film fabrication

Romero‐Angel, María; Castells‐Gil, Javier; Rubio‐Giménez, Víctor; Ameloot, Rob; Tatay, Sergio; Martí‐Gastaldo, Carlos

doi:10.1039/d1cc02828f

Cited by 4 publications

(7 citation statements)

References 30 publications

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“…Although nanoMOFs containing Ti-oxo and related Zr-oxo motifs have been previously prepared, [22][23][24] the smallest reported sizes typically range from 60 to 100 nm. To prepare MIL-125 particles suitable for solution-state techniques (sub-50 nm diameters), we adopted synthetic strategies that would allow efficient optimization of reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

Gram-scale synthesis of MIL-125 nanoparticles and their solution processability

et al. 2023

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Section: Resultsmentioning

confidence: 99%

Gram-scale synthesis of MIL-125 nanoparticles and their solution processability

et al. 2023

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“…MIL‐125NH 2 nanoparticles were prepared following a recently reported procedure. [ 46 ] 2‐aminoterephtalic acid (274.5 mg, 1.5 mmol), titanium isopropoxide Ti(OiPr) 4 (0.305 mL, 1 mmol), and dodecanoic acid (6.06 g, 30 mmol) were introduced in a solution of 20 mL of N,N ‐dimethylformamide (DMF) and 2.2 mL of dry methanol. The mixture was stirred gently for 5 min at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…The resulting composite helical structure is a highly integrated, magnetically driven MOF‐based microrobot (MOFBOT). [ 43,44 ] Our approach is successfully demonstrated with the following MOF nanocrystals (Figure S1, Supporting Information): Matériaux de l'Institut Lavoisier (MIL)‐100(Fe) (17 ± 2 nm), [ 45 ] MIL‐125NH 2 (93 ± 34 nm), [ 46 ] Universitetet I Oslo (UiO)‐66 (73 ± 12 nm), [ 47 ] and zeolitic imidazolate framework (ZIF)‐8 (755 ± 52 nm), [ 48a ] hereafter called MIL‐100(Fe)@MOFBOTs, MIL‐125NH 2 @MOFBOTs, UiO‐66@MOFBOTs, and ZIF‐8@MOFBOTs, respectively. To ensure a homogenous coverage of the bio‐templated magnetic chassis by MOF nanocrystals, the magnetic surface is functionalized with a thin layer of glycerol‐plasticized gelatin.…”

Section: Introductionmentioning

confidence: 99%

Biotemplating of Metal–Organic Framework Nanocrystals for Applications in Small‐Scale Robotics

Terzopoulou

Palacios‐Corella

Franco

et al. 2021

Adv Funct Materials

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Biotemplating is a powerful approach for manufacturing small-scale devices.Here, the assembly of metal-organic framework (MOF) nanocrystals onto biotemplated magnetic helical structures on the cyanobacterium Spirulina platensis is reported. It is demonstrated that the authors' approach is universal and can be used to equip biotemplated structures with different functional MOF systems. The successful assembly of MOF nanocrystals on magnetically coated helical biotemplates is achieved by decorating the magnetic surface with gelatin, a naturally occurring macromolecule with synthon moieties that allows anchoring of the MOF nanocrystals via electrostatic interactions. Furthermore, as gelatin is a thermally responsive material, it can serve to free the magnetic biotemplates from the MOF nanocrystal cargoes. As such, the systems can be used as highly integrated magnetically driven microrobots with multiple functionalities. To this end, the potential of these composite helical architectures is demonstrated as MOF-based small-scale robots with applications in biomedicine and environmental remediation.

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“…Furthermore, such distinct interior vs exterior redox behavior should become pronounced when the accessible surface of MOF exteriors and interiors become comparable, as with MOF nanocrystals . Interestingly, MOF nanocrystals exhibit improved ion-transport dynamics in contrast to the bulk alternatives and permit greater synthetic control over particle morphology and self-assembly, − opening fundamental investigations into structure–redox relationships. Conductive MOF nanocrystals with redox-active sites and nanoconfined pore environment therefore offer a unique platform for understanding intercalation chemistry in general.…”

Section: Introductionmentioning

confidence: 99%

Giant Redox Entropy in the Intercalation vs Surface Chemistry of Nanocrystal Frameworks with Confined Pores

et al. 2023

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Redox intercalation involves coupled ion-electron motion within host materials, finding extensive application in energy storage, electrocatalysis, sensing, and optoelectronics. Monodisperse MOF nanocrystals, compared to their bulk phases, exhibit accelerated mass transport kinetics that promote redox intercalation inside nanoconfined pores. However, nanosizing MOFs significantly increases their external surface-to-volume ratios, making the intercalation redox chemistry into MOF nanocrystals difficult to understand due to the challenge of differentiating redox sites at the exterior of MOF particles from the internal nanoconfined pores. Here, we report that Fe(1,2,3triazolate) 2 possesses an intercalation-based redox process shifted ca. 1.2 V from redox at the particle surface. Such distinct chemical environments do not appear in idealized MOF crystal structures but become magnified in MOF nanoparticles. Quartz crystal microbalance and time-of-flight secondary ion mass spectrometry combined with electrochemical studies identify the existence of a distinct and highly reversible Fe 2+ /Fe 3+ redox event occurring within the MOF interior. Systematic manipulation of experimental parameters (e.g., film thickness, electrolyte species, solvent, and reaction temperature) reveals that this feature arises from the nanoconfined (4.54 Å) pores gating the entry of charge-compensating anions. Due to the requirement for full desolvation and reorganization of electrolyte outside the MOF particle, the anion-coupled oxidation of internal Fe 2+ sites involves a giant redox entropy change (i.e., 164 J K −1 mol −1 ). Taken together, this study establishes a microscopic picture of ion-intercalation redox chemistry in nanoconfined environments and demonstrates the synthetic possibility of tuning electrode potentials by over a volt, with profound implications for energy capture and storage technologies.

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Surfactant-assisted synthesis of titanium nanoMOFs for thin film fabrication

Abstract: We use dodecanoic acid as a modulator to yield titanium MOF nanoparticles with good control of size and colloid stability and minimum impact to the properties of the framework to...

Cited by 4 publications

References 30 publications

Gram-scale synthesis of MIL-125 nanoparticles and their solution processability

Gram-scale synthesis of MIL-125 nanoparticles and their solution processability

Biotemplating of Metal–Organic Framework Nanocrystals for Applications in Small‐Scale Robotics

Giant Redox Entropy in the Intercalation vs Surface Chemistry of Nanocrystal Frameworks with Confined Pores

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