Adsorption of metal ions on nitrogen surface functional groups in activated carbons

A commercially available coconut-shell-derived active carbon was oxidized with nitric acid, and both the original and oxidized active carbons were treated with ammonia at 1073 K to incorporate nitrogen functional groups into the carbon. An active carbon with very high nitrogen content (similar to9.4 wt % daf) was also prepared from a nitrogen-rich precursor, polyacrylonitrile (PAN). These nitrogen-rich carbons had points of zero charge (pH(pzc)) similar to H-type active carbons. X-ray absorption near-edge structure (XANES) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and temperature-programmed desorption (TPD) were used to characterize the nitrogen functional groups in the carbons. The nitrogen functional groups present on the carbon surface were pyridinic, pyrrolic (or indolic), and pyridonic structures. The adsorption of transition metal cations Cd2+, Ni2+, and Cu2+ from aqueous solution on the suite of active carbons showed that adsorption was markedly higher for carbons with nitrogen functional groups present on the surface than for carbons with similar pH(pzc) values. In contrast, the adsorption characteristics of Ca2+ from aqueous solution were similar for all the carbons studied. Flow microcalorimetry (FMC) studies showed that the enthalpies of adsorption of Cd2+(aq) on the active carbons with high nitrogen contents were much higher than for nitric acid oxidized carbons studied previously, which also had enhanced adsorption characteristics for metal ion species. The enthalpies of adsorption of Cu2+ were similar to those obtained for Cd2+ for specific active carbons. The nitrogen functional groups in the carbons act as surface coordination sites for the adsorption of transition metal ions from aqueous solution. The adsorption characteristics of these carbons are compared with those of oxidized carbons.

Influence of solution chemistry on Cr(VI) reduction and complexation onto date-pits/tea-waste biomaterials

Tea waste (TW) and Date pits (DP) were investigated for their potential to remove toxic Cr(VI) ions from aqueous solution. Investigations showed that the majority of the bound Cr(VI) ions were reduced to Cr(III) after biosorption at acidic conditions. The electrons for the reduction of Cr(VI) may have been donated from the TW and DP biomasses. The experimental data obtained for Cr(VI)-TW and Cr(VI)-DP at different solution temperatures indicate a multilayer type biosorption, which explains why the Sips isotherm accurately represents the experimental data obtained in this study. The Sips maximum biosorption capacities of Cr(VI) onto TW and DP were 5.768 and 3.199 mmol/g at 333 K, respectively, which is comparatively superior to most other low-cost biomaterials. Fourier transform infrared spectroscopic analysis of the metal loaded biosorbents confirmed the participation of -COOH, -NH and O-CH groups in the reduction and complexation of chromium. Thermodynamic parameters demonstrated that the biosorption of Cr(VI) onto TW and DP biomass was endothermic, spontaneous and feasible at 303-333 K. The results evidently indicated that tea waste and date pits would be suitable biosorbents for Cr(VI) in wastewater under specific conditions.

DRIFTS/MS/Isotopic Labeling Study on the NO-Moderated Decomposition of a Silica-Supported Nickel Nitrate Catalyst Precursor

In the preparation of silica-supported nickel oxide from nickel nitrate impregnation and drying, the replacement of the traditional air calcination step by a thermal treatment in 1% NO/Ar prevents agglomeration, resulting in highly dispersed NiO. The mechanism by which NO prevents agglomeration was investigated by using combined in situ diffuse reflectance infrared fourier transform (DRIFT) spectroscopy and mass spectrometry (MS). After impregnation and drying, a supported nickel hydroxynitrate phase with composition Ni(3)(NO(3))(2)(OH)(4) had been formed. Comparison of the evolution of the decomposition gases during the thermal decomposition of Ni(3)(NO(3))(2)(OH)(4) in labeled and unlabeled NO and O(2) revealed that NO scavenges oxygen radicals, forming NO(2). The DRIFT spectra revealed that the surface speciation evolved differently in the presence of NO as compared with in O(2) or Ar. It is proposed that oxygen scavenging by NO depletes the Ni(3)(NO(3))(2)(OH)(4) phase of nitrate groups, creating nucleation sites for the formation of NiO, which leads to very small (similar to 4 nm) NiO particles and prevents agglomeration.

Plasma polymerization of 2-iodothiophene

Continuous wave rf plasma polymerization of 2-iodothiophene has been studied using X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), and Fourier transform infrared spectroscopy (FTIR). The variation in plasma polymer stoichiometry and the extent of monomer fragmentation are found to be critically dependent upon the electrical discharge power.

The water-gas shift reaction over CeO/CuO:Operando SSITKA-DRIFTS-mass spectrometry study of low temperature mechanism

An inverse CeO2/CuO catalyst has been investigated by operando steady-state isotopic transient kinetic analysis (SSITKA) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under 3% CO +3% H2O reactant mixture at 473 K with the aim of determining intermediates involved in the water gas shift reaction at relatively low temperatures. Among the various species detected in the infrared spectra which may be involved in the reaction, i.e. formates, copper carbonyls and carbonates, a particular type of carbonate species is identified as a reaction intermediate on the basis of detailed analysis of the spectra during isotopic exchange in comparison with the change in the corresponding isotopically labelled CO2 product. 

Observation of an optical phonon band in situ in TiO electrochemistry:A possible indicator of strongly trapped intermediates in the O evolution reaction

This Letter reports in situ Fourier transform infrared (FTIR) spectroscopic data on thermal TiO films fabricated by heating titanium plates in air at 475, 700 and 800 °C. The films were studied in the dark and under UV-irradiation in aqueous 0.1MNaClO in the presence and absence of 0.1 M Na(OOC) and at 10, 25 and 50 °C. The film fabricated at 800 °C showed a broad feature near 1580cm under UV-irradiation that was not observed in the dark, whilst the films fabricated at lower temperatures, 475 and 700 °C, showed no such feature. This feature appears to be associated with the accumulation of surface-mobile holes at the complex, porous film-electrolyte interface and the capacity of such holes to enhance the absorption cross-section of optical phonons characteristic of the rutile crystal form at and near the surface of the TiO/electrolyte interface. © 2001 Elsevier Science B.V.

On-line FTIR spectroscopic investigations of methanol oxidation in a direct methanol fuel cell

A real-time Fourier transform infrared spectroscopy (FTIRS) analysis of the products of methanol oxidation in a prototype direct-methanol fuel cell operating at high temperatures (150 to 185°C) is reported here. The methanol oxidation products on platinum black and platinum-ruthenium catalyst surfaces were determined as a function of the fuel cell operating temperature, current density, and methanol/water mole ratio. Neither formaldehyde nor formic acid was detected in anode exhaust gas at all cell operating conditions. The product distributions of methanol oxidation obtained by on-line FTIRS are consistent with our previous results obtained by on-line mass spectroscopy under similar conditions. With pure methanol in anode feed, methanaldimethylacetal was found to be the main product, methyl formate and CO were also found. However, when water was present in the anode feed, the main product was CO , and the formation of methanaldimethylacetal and methyl formate decreased significantly with increase of the water/methanol mole ratio. Increase of cell operating temperature enhanced the formation of CO and decreased the formation of methanaldimethylacetal and methyl formate. Pt/Ru catalyst is more active for methanol oxidation and has a higher selectivity toward CO formation than Pt-black. Nearly complete methanol oxidation, i.e., the product was almost exclusively CO , was achieved using a Pt/Ru catalyst and a water/methanol mole ratio of 2 or higher in the anode feed at a temperature of 185°C or above.

The Impact of Wind Farm Power Oscillations on the Irish Power System

The impact of power fluctuations arising from fixed-speed wind turbines on the magnitude and frequency of inter-area oscillations has been investigated. The authors introduced data acquisition equipment to record the power flow on the interconnector between the Northern Ireland and Republic of Ireland systems. Through monitoring the interconnector oscillation using a fast Fourier transform, it was possible to determine the magnitude and frequency of the inter-area oscillation between the two systems. The impact of tower shadow on the output power from a wind farm was analysed using data recorded on site. A case study investigates the effect on the system of the removal of a large fixed-speed wind farm. Conclusions are drawn on the impact that conventional generation and the output from fixed-speed wind farms have on the stability of the Irish power system.

Wind Farm Induced Oscillations

The impact of power fluctuations arising from fixed-speed wind turbines on the magnitude and frequency of inter-area oscillations was investigated. The authors used data acquisition equipment to record the power flow on the interconnector between the Northern Ireland and Republic of Ireland systems. By monitoring the interconnector oscillation using a fast Fourier transform, it was possible to determine the magnitude and frequency of the inter-area oscillation between the Northern Ireland electricity system and that of the electricity supply board. Analysis was preformed to determine the relationship (if any) between the inter-area oscillation and the observed wind power generation at the corresponding time. Subsequently, regression analysis was introduced to model this relationship between the FFT output and the wind power generation. The effect of conventional generators on the magnitude and frequency of the inter-area oscillation was also considered.