Abstract: Here, we report a simple method for the direct conversion of 6-Nitro-1H-indole into N-substituted indoles via electrochemical dehydrogenative reaction with halogenated reagents under strongly basic conditions through N–R bond formation. The N-protected indoles have been prepared under moderate and scalable electrolytic conditions. The conduct of the reactions was performed in a simple divided cell under constant current without oxidizing reagents or transition-metal catalysts. The synthesized products have been characterized via UV/Vis spectrophotometry, 1H-NMR, and FTIR spectroscopy. A possible reaction mechanism is discussed based on the N-protective products. This methodology could be applied to the synthesis of various biologically active N-substituted indole derivatives.
Abstract: Single-walled carbon nanotubes (SWCNTs) are generally synthesized by chemical vapor deposition (CVD) using Fe, Co, and Ni as catalysts. However, due to the Ostwald ripening of metal catalysts, the diameter distribution of the grown SWCNTs is considerably wide (>2 nm), which is not suitable for electronics applications. In addition, reduction in the growth temperature is desirable for fabricating SWCNT devices compatible with the LSI process. Herein, we performed SWCNT growth by alcohol catalytic CVD using platinum-group metal catalysts (Pt, Rh, and Pd) because these metals have high melting points, and the reduction in the Ostwald ripening of catalyst particles is expected. Our results revealed that web-like SWCNTs were obtained from Pt and Rh catalysts at growth temperature between 500 °C and 600 °C by optimizing the ethanol pressure. The SWCNT yield from Pd catalysts was considerably low. By decreasing the growth temperature, the diameter and chirality distribution of SWCNTs from Pt and Rh catalysts became small and narrow. In particular, the diameters of most SWCNTs grown using Pt catalysts were below 1 nm and their diameter distribution was considerably narrow. On the contrary, SWCNTs can grow from Rh catalysts even at 300 °C by optimizing the growth condition, which is the lowest temperature recorded for SWCNT growth. Our results demonstrated that platinum-group metals are useful for the growth of small-diameter SWCNTs and facilitate low-temperature growth.
Abstract: Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H2) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H2, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.
Abstract: PLA emerged as a promising polymer because of its
property as a compostable, biodegradable thermoplastic made from
renewable sources. PLA can be polymerized from monomers
(Lactide or Lactic acid) obtained by fermentation processes from
renewable sources such as corn starch or sugarcane. For PLA
synthesis, ring opening polymerization (ROP) of Lactide monomer is
one of the preferred methods. In the literature, the technique mainly
developed for ROP of PLA is based on metal/bimetallic catalyst (Sn,
Zn and Al) or other organic catalysts in suitable solvent. However,
the PLA synthesized using such catalysts may contain trace elements
of the catalyst which may cause toxicity. This work estimated the
usefulness and drawbacks of using different catalysts as well as effect
of alternative energies and future aspects for PLA production.
Abstract: The supported Pd catalysts were analyzed by X-ray
diffraction and X-ray absorption spectroscopy in order to determine
their global and local structure. The average particle size of the
supported Pd catalysts was determined by X-ray diffraction method.
One of the main purposes of the present contribution is to focus on
understanding the specific role of the Pd particle size determined by
X-ray diffraction and that of the support oxide. Based on X-ray
absorption fine structure spectroscopy analysis we consider that the
whole local structure of the investigated samples are distorted
concerning the atomic number but the distances between atoms are
almost the same as for standard Pd sample. Due to the strong
modifications of the Pd cluster local structure, the metal-support
interface may influence the electronic properties of metal clusters
and thus their reactivity for absorption of the reactant molecules.
Abstract: carbonylation of methanol in homogenous phase is
one of the major routesfor production of acetic acid. Amongst group
VIII metal catalysts used in this process iridium has displayed the
best capabilities. To investigate effect of operating parameters like:
temperature, pressure, methyl iodide, methyl acetate, iridium,
ruthenium, and water concentrations on the reaction rate,
experimental design for this system based upon central composite
design (CCD) was utilized. Statistical rate equation developed by this
method contained individual, interactions and curvature effects of
parameters on the reaction rate. The model with p-value less than
0.0001 and R2 values greater than 0.9; confirmeda satisfactory fitness
of the experimental and theoretical studies. In other words, the
developed model and experimental data obtained passed all
diagnostic tests establishing this model as a statistically significant.
Abstract: The nickel and gold nanoclusters as supported
catalysts were analyzed by XAS, XRD and XPS in order to
determine their local, global and electronic structure. The present
study has pointed out a strong deformation of the local structure of
the metal, due to its interaction with oxide supports. The average
particle size, the mean squares of the microstrain, the particle size
distribution and microstrain functions of the supported Ni and Au
catalysts were determined by XRD method using Generalized Fermi
Function for the X-ray line profiles approximation. Based on EXAFS
analysis we consider that the local structure of the investigated
systems is strongly distorted concerning the atomic number pairs.
Metal-support interaction is confirmed by the shape changes of the
probability densities of electron transitions: Ni K edge (1s →
continuum and 2p), Au LIII-edge (2p3/2 → continuum, 6s, 6d5/2 and
6d3/2). XPS investigations confirm the metal-support interaction at
their interface.
Abstract: In this study, multiwall carbon nanotubes (MWNTs)
were modified with nitric acid chemically and by dielectric barrier
discharge (DBD) plasma in an oxygen-based atmosphere. Used
carbon nanotubes (CNTs) were prepared by chemical vapour
deposition (CVD) floating catalyst method. For removing amorphous
carbon and metal catalyst, MWNTs were exposed to dry air and
washed with hydrochloric acid. Heating purified CNTs under helium
atmosphere caused elimination of acidic functional groups. Fourier
transformed infrared spectroscopy (FTIR) shows formation of
oxygen containing groups such as C=O and COOH. Brunauer,
Emmett, Teller (BET) analysis revealed that functionalization causes
generation of defects on the sidewalls and opening of the ends of
CNTs. Results of temperature-programmed desorption (TPD) and gas
chromatography(GC) indicate that nitric acid treatment create more
acidic groups than plasma treatment.
Abstract: Carbon nanotubes (CNTs) possess unique structural,
mechanical, thermal and electronic properties, and have been
proposed to be used for applications in many fields. However, to
reach the full potential of the CNTs, many problems still need to be
solved, including the development of an easy and effective
purification procedure, since synthesized CNTs contain impurities,
such as amorphous carbon, carbon nanoparticles and metal particles.
Different purification methods yield different CNT characteristics
and may be suitable for the production of different types of CNTs. In
this study, the effect of different purification chemicals on carbon
nanotube quality was investigated. CNTs were firstly synthesized by
chemical vapor deposition (CVD) of acetylene (C2H2) on a
magnesium oxide (MgO) powder impregnated with an iron nitrate
(Fe(NO3)3·9H2O) solution. The synthesis parameters were selected
as: the synthesis temperature of 800°C, the iron content in the
precursor of 5% and the synthesis time of 30 min. The liquid phase
oxidation method was applied for the purification of the synthesized
CNT materials. Three different acid chemicals (HNO3, H2SO4, and
HCl) were used in the removal of the metal catalysts from the
synthesized CNT material to investigate the possible effects of each
acid solution to the purification step. Purification experiments were
carried out at two different temperatures (75 and 120 °C), two
different acid concentrations (3 and 6 M) and for three different time
intervals (6, 8 and 15 h). A 30% H2O2 : 3M HCl (1:1 v%) solution
was also used in the purification step to remove both the metal
catalysts and the amorphous carbon. The purifications using this
solution were performed at the temperature of 75°C for 8 hours.
Purification efficiencies at different conditions were evaluated by
thermogravimetric analysis. Thermal and electrical properties of
CNTs were also determined. It was found that the obtained electrical
conductivity values for the carbon nanotubes were typical for organic
semiconductor materials and thermal stabilities were changed
depending on the purification chemicals.
Abstract: Silver nano-particles have been used for antibacterial
purpose and it is also believed to have removal of odorous compounds,
oxidation capacity as a metal catalyst. In this study, silver
nano-particles in nano sizes (5-30 nm) were prepared on the surface of
NaHCO3, the supporting material, using a sputtering method that
provided high silver content and minimized conglomerating problems
observed in the common AgNO3 photo-deposition method. The silver
nano-particles were dispersed by dissolving Ag-NaHCO3 into water,
and the dispersed silver nano-particles in the aqueous phase were
applied to remove inorganic odor compounds, H2S, in a scrubbing
reactor. Hydrogen sulfide in the gas phase was rapidly removed by the
silver nano-particles, and the concentration of sulfate (SO4
2-) ion
increased with time due to the oxidation reaction by silver as a
catalyst. Consequently, the experimental results demonstrated that the
silver nano-particles in the aqueous solution can be successfully
applied to remove odorous compounds without adding additional
energy sources and producing any harmful byproducts
Abstract: The aim of this study was to synthesize the single
walled carbon nanotubes (SWCNTs) and determine their hydrogen
storage capacities. SWCNTs were firstly synthesized by chemical
vapor deposition (CVD) of acetylene (C2H2) on a magnesium oxide
(MgO) powder impregnated with an iron nitrate (Fe(NO3)3·9H2O)
solution. The synthesis parameters were selected as: the synthesis
temperature of 800°C, the iron content in the precursor of 5% and the
synthesis time of 30 min. Purification process of SWCNTs was
fulfilled by microwave digestion at three different temperatures (120,
150 and 200 °C), three different acid concentrations (0.5, 1 and 1.5
M) and for three different time intervals (15, 30 and 60 min). Nitric
acid (HNO3) was used in the removal of the metal catalysts. The
hydrogen storage capacities of the purified materials were measured
using volumetric method at the liquid nitrogen temperature and gas
pressure up to 100 bar. The effects of the purification conditions such
as temperature, time and acid concentration on hydrogen adsorption
were investigated.