Non-oxidative Coupling of Methane to Ethylene Using Mo2 C/[B]ZSM-5.

Methane non-oxidative coupling to ethylene was investigated on Mo2 C/[B]ZSM-5 catalyst at 923 K and atmospheric pressure. In contrast to Mo2 C/[Al]ZSM-5 catalysts for methane aromatization, this material exhibits very high ethylene selectivity (>90 %) and low aromatics (benzene and naphthalene) selectivity. The much weaker Brønsted acidity of [B]ZSM-5 leads to a slow rate of ethylene oligomerization. The stability of the catalyst is greatly enhanced with 93 % of the initial reaction rate remaining after 18 h of time on stream. In-situ UV/VIS spectra indicate that prior to carburization, mono/binuclear Mo oxides are initially well dispersed onto the zeolite support. Mo carbides clusters, formed during carburization with methane, appear similar to clusters formed in [Al]ZSM-5, as indicated by the X-ray Absorption Spectroscopy (XAS) data.

Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods.

The non-centrosymmetry requirement of sum frequency generation (SFG) vibration spectroscopy allows the detection and quantification of crystalline cellulose in lignocellulose biomass without spectral interferences from hemicelluloses and lignin. This paper shows a correlation between the amount of crystalline cellulose in biomass and the SFG signal intensity. Model biomass samples were prepared by mixing commercially available cellulose, xylan, and lignin to defined concentrations. The SFG signal intensity was found sensitive to a wide range of crystallinity, but varied non-linearly with the mass fraction of cellulose in the samples. This might be due to the matrix effects such as light scattering and absorption by xylan and lignin, as well as the non-linear density dependence of the SFG process itself. Comparison with other techniques such as XRD, FT-Raman, FT-IR and NMR demonstrate that SFG can be a complementary and sensitive tool to assess crystalline cellulose in biomass.

Selective detection of crystalline cellulose in plant cell walls with sum-frequency-generation (SFG) vibration spectroscopy.

The selective detection of crystalline cellulose in biomass was demonstrated with sum-frequency-generation (SFG) vibration spectroscopy. SFG is a second-order nonlinear optical response from a system where the optical centrosymmetry is broken. In secondary plant cell walls that contain mostly cellulose, hemicellulose, and lignin with varying concentrations, only certain vibration modes in the crystalline cellulose structure can meet the noninversion symmetry requirements. Thus, SFG can be used to detect and analyze crystalline cellulose selectively in lignocellulosic biomass without extraction of noncellulosic species from biomass or deconvolution of amorphous spectra. The selective detection of crystalline cellulose in lignocellulosic biomass is not readily achievable with other techniques such as XRD, solid-state NMR, IR, and Raman analyses. Therefore, the SFG analysis presents a unique opportunity to reveal the cellulose crystalline structure in lignocellulosic biomass.