Ultrafast photoelectron spectroscopy of photoexcited aqueous ferrioxalate

2021 ◽  
Author(s):  
Luca Longetti ◽  
Thomas Roland Barillot ◽  
Michele Puppin ◽  
José Ojeda ◽  
Luca Poletto ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Photoelectron Spectroscopy ◽  
Relaxation Processes ◽  
Molecular Relaxation ◽  
Metal Organic ◽  
And Control

The photochemistry of metal-organic compounds in solution is determined by both intra- and inter-molecular relaxation processes after photoexcitation, and understanding its prime mechanisms is crucial to optimise it and control...

Green Synthesis and Enhanced CO2 Capture Performance of Perfluorinated Cerium-Based Metal-Organic Frameworks with UiO-66 and MIL-140 Topology

2018 ◽  
Author(s):  
Roberto D’Amato ◽  
Anna Donnadio ◽  
Mariolino Carta ◽  
Claudio Sangregorio ◽  
Riccardo Vivani ◽  
...  
Keyword(s):  
Photoelectron Spectroscopy ◽  
Metal Organic Frameworks ◽  
Isosteric Heat ◽  
Experimental Conditions ◽  
Cerium Ammonium Nitrate ◽  
Ideal Adsorbed Solution Theory ◽  
Metal Organic ◽  
Adsorbed Solution ◽  
Better Than ◽  
The Ideal

Reaction of cerium ammonium nitrate and tetrafluoroterephthalic acid in water afforded two new metal-organic frameworks with UiO-66 [F4_UiO-66(Ce)] and MIL-140 [F4_MIL-140A(Ce)] topologies. The two compounds can be obtained in the same experimental conditions, just by varying the amount of acetic acid used as crystallization modulator in the synthesis. Both F4_UiO-66(Ce) and F4_MIL-140A(Ce) feature pores with size < 8 Å, which classifies them as ultramicroporous. Combination of X-ray photoelectron spectroscopy and magnetic susceptibility measurements revealed that both compounds contain a small amount of Ce(III), which is preferentially accumulated near the surface of the crystallites. The CO<sub>2</sub> sorption properties of F4_UiO-66(Ce) and F4_MIL-140A(Ce) were investigated, finding that they perform better than their Zr-based analogues. F4_MIL-140A(Ce) displays an unusual S-shaped isotherm with steep uptake increase at pressure < 0.2 bar at 298 K. This makes F4_MIL-140A(Ce) exceptionally selective for CO<sub>2</sub> over N<sub>2</sub>: the calculated selectivity, according to the ideal adsorbed solution theory for a 0.15:0.85 mixture at 1 bar and 293 K, is higher than 1900, amongst the highest ever reported for metal-organic frameworks. The calculated isosteric heat of CO<sub>2 </sub>adsorption is in the range of 38-40 kJ mol<sup>-1</sup>, indicating a strong physisorptive character.

Kinetic Control of Interpenetration in Fe-Biphenyl-4,4′-dicarboxylate MOFs by Coordination and Oxidation Modulation

2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  
Keyword(s):  
Self Assembly ◽  
Surface Areas ◽  
Metal Precursors ◽  
Additional Coordination ◽  
Fine Control ◽  
Multiple Alternative ◽  
Metal Organic ◽  
Dft Simulations ◽  
High Valent ◽  
And Control

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>

scholarly journals Photocatalytic reduction of graphene oxide with cuprous oxide film under UV-vis irradiation

2020 ◽  
Vol 59 (1) ◽  
pp. 207-214 ◽  
Author(s):  
Yao Wang ◽  
Jianqing Feng ◽  
Lihua Jin ◽  
Chengshan Li
Keyword(s):  
Graphene Oxide ◽  
Photoelectron Spectroscopy ◽  
Low Cost ◽  
Photocatalytic Reduction ◽  
Force Microscopy ◽  
Atomic Force ◽  
Reduced Graphene ◽  
Reduction Efficiency ◽  
Metal Organic ◽  
Reduction Effect

AbstractWe have grown Cu2O films by different routes including self-oxidation and metal-organic deposition (MOD). The reduction efficiency of Cu2O films on graphene oxide (GO) synthesized by modified Hummer’s method has been studied. Surface morphology and chemical state of as-prepared Cu2O film and GO sheets reduced at different conditions have also been investigated using atomic force microscopy (AFM) and x-ray photoelectron spectroscopy (XPS). Results show that self-oxidation Cu2O film is more effective on phtocatalytic reduction of GO than MOD-Cu2O film. Moreover, reduction effect of self-oxidation Cu2O film to GO is comparable to that of environmental-friendly reducing agent of vitamin C. The present results offer a potentially eco-friendly and low-cost approach for the manufacture of reduced graphene oxide (RGO) by photocatalytic reduction.

scholarly journals Volatile Organic Compound Vapour Measurements Using a Localised Surface Plasmon Resonance Optical Fibre Sensor Decorated with a Metal-Organic Framework

Sensors ◽  
2021 ◽  
Vol 21 (4) ◽  
pp. 1420
Author(s):  
Chenyang He ◽  
Liangliang Liu ◽  
Sergiy Korposh ◽  
Ricardo Correia ◽  
Stephen P. Morgan
Keyword(s):  
Surface Plasmon Resonance ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Surface Plasmon ◽  
Optical Fibre ◽  
Plasmon Resonance ◽  
Metal Organic Framework ◽  
Volatile Organic ◽  
Metal Organic ◽  
Organic Framework

A tip-based fibreoptic localised surface plasmon resonance (LSPR) sensor is reported for the sensing of volatile organic compounds (VOCs). The sensor is developed by coating the tip of a multi-mode optical fibre with gold nanoparticles (size: 40 nm) via a chemisorption process and further functionalisation with the HKUST-1 metal–organic framework (MOF) via a layer-by-layer process. Sensors coated with different cycles of MOFs (40, 80 and 120) corresponding to different crystallisation processes are reported. There is no measurable response to all tested volatile organic compounds (acetone, ethanol and methanol) in the sensor with 40 coating cycles. However, sensors with 80 and 120 coating cycles show a significant redshift of resonance wavelength (up to ~9 nm) to all tested volatile organic compounds as a result of an increase in the local refractive index induced by VOC capture into the HKUST-1 thin film. Sensors gradually saturate as VOC concentration increases (up to 3.41%, 4.30% and 6.18% in acetone, ethanol and methanol measurement, respectively) and show a fully reversible response when the concentration decreases. The sensor with the thickest film exhibits slightly higher sensitivity than the sensor with a thinner film. The sensitivity of the 120-cycle-coated MOF sensor is 13.7 nm/% (R2 = 0.951) with a limit of detection (LoD) of 0.005% in the measurement of acetone, 15.5 nm/% (R2 = 0.996) with an LoD of 0.003% in the measurement of ethanol and 6.7 nm/% (R2 = 0.998) with an LoD of 0.011% in the measurement of methanol. The response and recovery times were calculated as 9.35 and 3.85 min for acetone; 5.35 and 2.12 min for ethanol; and 2.39 and 1.44 min for methanol. The humidity and temperature crosstalk of 120-cycle-coated MOF was measured as 0.5 ± 0.2 nm and 0.5 ± 0.1 nm in the humidity range of 50–75% relative humidity (RH) and temperature range of 20–25 °C, respectively.

scholarly journals Fabrication of Carboxymethylcellulose/Metal-Organic Framework Beads for Removal of Pb(II) from Aqueous Solution

Materials ◽  
2019 ◽  
Vol 12 (6) ◽  
pp. 942 ◽  
Author(s):  
Huo-Xi Jin ◽  
Hong Xu ◽  
Nan Wang ◽  
Li-Ye Yang ◽  
Yang-Guang Wang ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Adsorption Capacity ◽  
Photoelectron Spectroscopy ◽  
Langmuir Isotherm ◽  
Adsorption Equilibrium ◽  
Isotherm Model ◽  
Maximum Adsorption Capacity ◽  
X Ray ◽  
Metal Organic ◽  
Langmuir Isotherm Model

The ability to remove toxic heavy metals, such as Pb(II), from the environment is an important objective from both human-health and ecological perspectives. Herein, we describe the fabrication of a novel carboxymethylcellulose-coated metal organic material (MOF-5–CMC) adsorbent that removed lead ions from aqueous solutions. The adsorption material was characterized by Fourier-transform infrared spectroscopy, X-ray diffractometry, scanning electron microscopy, and X-ray photoelectron spectroscopy. We studied the functions of the contact time, pH, the original concentration of the Pb(II) solution, and adsorption temperature on adsorption capacity. MOF-5–CMC beads exhibit good adsorption performance; the maximum adsorption capacity obtained from the Langmuir isotherm-model is 322.58 mg/g, and the adsorption equilibrium was reached in 120 min at a concentration of 300 mg/L. The adsorption kinetics is well described by pseudo-second-order kinetics, and the adsorption equilibrium data are well fitted to the Langmuir isotherm model (R2 = 0.988). Thermodynamics experiments indicate that the adsorption process is both spontaneous and endothermic. In addition, the adsorbent is reusable. We conclude that MOF-5–CMC is a good adsorbent that can be used to remove Pb(II) from aqueous solutions.

scholarly journals Highly Efficient Adsorption of Aqueous Pb(II) with Mesoporous Metal-Organic Framework-5: An Equilibrium and Kinetic Study

2016 ◽  
Vol 2016 ◽  
pp. 1-9 ◽  
Author(s):  
José María Rivera ◽  
Susana Rincón ◽  
Cherif Ben Youssef ◽  
Alejandro Zepeda
Keyword(s):  
Kinetic Study ◽  
Photoelectron Spectroscopy ◽  
Metal Organic Framework ◽  
Isotherm Models ◽  
Ionic Exchange ◽  
Order Kinetic ◽  
X Ray ◽  
Metal Organic ◽  
Mesoporous Metal ◽  
Organic Framework

Mesoporous metal-organic framework-5 (MOF-5), with the composition Zn4O(BDC)3, showed a high capacity for the adsorptive removal of Pb(II) from 100% aqueous media. After the adsorption process, changes in both morphology and composition were detected using a scanning electron microscope (SEM) equipped with an energy dispersive X-ray (EDX) system, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) analysis. The experimental evidence showed that Zn(II) liberation from MOF-5 structure was provoked by the water effect demonstrating that Pb(II) removal is not due to ionic exchange with Zn. A kinetic study showed that Pb(II) removal was carried out in 30 min with a behavior of pseudo-second-order kinetic model. The experimental data on Pb(II) adsorption were adequately fit by both the Langmuir and BET isotherm models with maximum adsorption capacities of 658.5 and 412.7 mg/g, respectively, at pH 5 and 45°C. The results of this work demonstrate that the use of MOF-5 has great potential for applications in environmental protection, especially regarding the removal of the lead present in industrial wastewaters and tap waters.

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