Sumit Sachdeva

Probing hydrogen spillover in Pd@MIL-101(Cr) with a focus on hydrogen chemisorption

Palladium nanoparticles can split the dihydrogen bond and produce atomic hydrogen. When the metal nanoparticles are in intimate contact with a hydrogen-atom host, chemisorption of H-atoms by the host has been suggested to occur via the hydrogen spillover mechanism. Metal-organic frameworks were predicted to be able to act as effective chemisorption sites, and increased ambient-temperature hydrogen adsorption was reported on several occasions. The intimate contact was supposedly ensured by the use of a carbon bridge. In this work, we show that it is possible to introduce catalyst palladium particles into MOFs pores and simultaneously ensuring good contact, making the employment of the carbon bridge redundant. The addition of Pd nanoparticles indeed increases the ambient-temperature hydrogen uptake of the framework, but this is found to be solely due to palladium hydride formation. In addition, we show that the hydrogen atoms do not chemisorb on the host framework, which excludes the possibility of hydrogen spillover.

Polymer‐Induced Surface Modifications of Pd‐based Thin Films Leading to Improved Kinetics in Hydrogen Sensing and Energy Storage Applications

The catalytic properties of Pd alloy thin films are enhanced by a thin sputtered PTFE coating, resulting in profound improvements in hydrogen adsorption and desorption in Pd-based and Pd-catalyzed hydrogen sensors and hydrogen storage materials. The remarkably enhanced catalytic performance is attributed to chemical modifications of the catalyst surface by the sputtered PTFE leading to a possible change in the binding strength of the intermediate species involved in the hydrogen sorption process.

Hydrogen termination of CVD diamond films by high-temperature annealing at atmospheric pressure

A high-temperature procedure to hydrogenate diamond films using molecular hydrogen at atmospheric pressure was explored. Undoped and doped chemical vapour deposited (CVD) polycrystalline diamond films were treated according to our annealing method using a H2 gas flow down to ~50 ml∕min (STP) at ~850 °C. The films were extensively evaluated by surface wettability, electron affinity, elemental composition, photoconductivity, and redox studies. In addition, electrografting experiments were performed. The surface characteristics as well as the optoelectronic and redox properties of the annealed films were found to be very similar to hydrogen plasma-treated films. Moreover, the presented method is compatible with atmospheric pressure and provides a low-cost solution to hydrogenate CVD diamond, which makes it interesting for industrial applications. The plausible mechanism for the hydrogen termination of CVD diamond films is based on the formation of surface carbon dangling bonds and carbon-carbon unsaturated bonds at the applied tempera-ture, which react with molecular hydrogen to produce a hydrogen-terminated surface.

Gas phase sensing of alcohols by Metal Organic Framework – polymer composite materials

Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0–100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing the promise of this type of chemical sensors.

Control of interpenetration of copper-based MOFs on supported surfaces by electrochemical synthesis

A study of a copper-based metal–organic framework (MOF) synthesized by an electrochemical route is presented. Morphological and adsorption properties of the MOF synthesized as bulk powder and on supported copper surfaces were investigated. Differences in these properties and structural refinement studies indicate that when 4,4′,4′′-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB) is used as linker interpenetration can be prevented when the structure is grown on a surface.

Sensitive and Reversible Detection of Methanol and Water Vapor by In Situ Electrochemically Grown CuBTC MOFs on Interdigitated Electrodes

The in situ electrochemical growth of Cu benzene-1,3,5-tricarboxylate (CuBTC) metal-organic frameworks, as an affinity layer, directly on custom-fabricated Cu interdigitated electrodes (IDEs) is described, acting as a transducer. Crystalline 5-7 µm thick CuBTC layers are grown on IDEs consisting of 100 electrodes with a width and a gap of both 50 µm and a height of 6-8 µm. These capacitive sensors are exposed to methanol and water vapor at 30 °C. The affinities show to be completely reversible with higher affinity toward water compared to methanol. For exposure to 1000 ppm methanol, a fast response is observed with a capacitance change of 5.57 pF at equilibrium. The capacitance increases in time followed diffusion-controlled kinetics (k = 2.9 mmol s-0.5 g-1CuBTC ). The observed capacitance change with methanol concentration follows a Langmuir adsorption isotherm, with a value for the equilibrium affinity Ke = 174.8 bar-1 . A volume fraction fMeOH = 0.038 is occupied upon exposure to 1000 ppm of methanol. The thin CuBTC affinity layer on the Cu-IDEs shows fast, reversible, and sensitive responses to methanol and water vapor, enabling quantitative detection in the range of 100-8000 ppm.

Contactless photoconductance study on undoped and doped nanocrystalline diamond films.

Hydrogen and oxygen surface-terminated nanocrystalline diamond (NCD) films are studied by the contactless time-resolved microwave conductivity (TRMC) technique and X-ray photoelectron spectroscopy (XPS). The optoelectronic properties of undoped NCD films are strongly affected by the type of surface termination. Upon changing the surface termination from oxygen to hydrogen, the TRMC signal rises dramatically. For an estimated quantum yield of 1 for sub-bandgap optical excitation the hole mobility of the hydrogen-terminated undoped NCD was found to be ∼0.27 cm(2)/(V s) with a lifetime exceeding 1 μs. Assuming a similar mobility for the oxygen-terminated undoped NCD a lifetime of ∼100 ps was derived. Analysis of the valence band spectra obtained by XPS suggests that upon oxidation of undoped NCD the surface Fermi level shifts (toward an increased work function). This shift originates from the size and direction of the electronic dipole moment of the surface atoms, and leads to different types of band bending at the diamond/air interface in the presence of a water film. In the case of boron-doped NCD no shift of the work function is observed, which can be rationalized by pinning of the Fermi level. This is confirmed by TRMC results of boron-doped NCD, which show no dependency on the surface termination. We suggest that photoexcited electrons in boron-doped NCD occupy nonionized boron dopants, leaving relatively long-lived mobile holes in the valence band.

Nanosheets of Nonlayered Aluminum Metal-Organic Frameworks through a Surfactant-Assisted Method

During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant-assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al-containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.

Fe3O4 nanoparticles coated with a guanidinium-functionalized polyelectrolyte extend the pH range for phosphate binding

In this work commercially available Fe3O4 NPs were coated with polyallylamine hydrochloride (PAH) and PAH functionalized with guanidinium groups (PAH–Gu) for investigating the phosphate adsorption properties under alkaline conditions. The coating can be prepared easily and rapidly and results in Fe3O4 NPs with improved properties related to phosphate binding and colloidal stability. At a low initial phosphate concentration (2 mg L−1), the novel Fe3O4@PAH–Gu material was able to remove phosphate rather independently of the pH condition (4.0, 3.6 and 3.7 mg g−1 at pH = 5, 8 and 10, respectively), whereas for the uncoated Fe3O4 NPs the amount of adsorbed phosphate drops by >75% upon changing from acidic to alkaline conditions (0.84 mg g−1 at pH = 10). Under alkaline conditions, the fastest adsorption was observed for Fe3O4@PAH–Gu followed by Fe3O4@PAH and Fe3O4. This can be related to the additional interaction forces due to the presence of primary amine groups (in PAH and PAH–Gu) and Gu groups (in PAH–Gu only) in coatings. Over 80% of the phosphate adsorbed on the novel Fe3O4@PAH–Gu material was successfully desorbed and the coated NPs were re-used over three adsorption/desorption cycles. This work will stimulate the design and preparation of functionalized polyelectrolytes for an extended area of applications, especially for the selective removal of target compounds from wastewater.