Singfoong Cheah

Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

Effects of thermal pretreatment and catalyst on biomass gasification efficiency and syngas composition

This work explores the combined effects of thermal pretreatment and using a catalyst in situ on gasification carbon conversion efficiency, as well as product gas and tar content and compositions. To compare the effects of thermal pretreatment, pelletized and ground oak with three different levels of thermal pretreatment were gasified in a fluidized bed reactor. The pretreatments applied to the oak were (1) pelletization, (2) drying at 180 °C in air, and (3) torrefaction at 270 °C in nitrogen. The oak dried at 180 °C produced syngas of similar quality and approximately the same amount of char as untreated oak. Torrefaction at 270 °C resulted in syngas with a higher hydrogen to CO ratio, lower methane, and less than half of the total tar—all of which are desirable properties in terms of product gas quality. However, the oak torrefied at 270 °C also produced more than two times the amount of char as the untreated, pelletized oak. To determine the effect of catalyst, a series of experiments were conducted using olivine impregnated with nickel and cerium as the fluidized bed material in the gasifier. These tests showed that modified olivine can improve hydrogen production and reduce methane and tar levels in the syngas. The result was observed for both treated and untreated oak; although the effect was more substantial for untreated oak, for which the use of modified olivine reduced tar concentrations in the product gas by 60%, with a larger reduction in heavier tars than lighter tars. This result is important because reduction in heavier tar plays a more important role in benefitting downstream operations.

Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Kα XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.