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Total photoyield experiments are applied to characterize p-, intrinsic, and n-type diamond with hydrogen-terminated surfaces. On all hydrogen-terminated samples a photoelectron threshold energy of 4.4 eV is detected which is discussed in detail in this letter. We attribute this threshold to the energy gap between the valence-band maximum and the vacuum level, which is 1.1 eV below the conduction-band minimum, and generally referred to as ”negative electron affinity” (NEA). Hydrogen terminated p-type and intrinsic diamond show a rise of secondary photoyield in the excitation regime hν>5.47eV. However, this is not detected on n-type diamond. We ascribe this to the formation of an upward surface band bending in the vicinity of the n-type diamond surface which acts as an energy barrier for electrons.

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We have developed an environmentally benign large-scale (50 kg wood meal per batch) lignin production plant, operating based on acid-catalyzed polyethylene glycol (PEG) solvolysis of softwood biomass. The motivation for the proposed process was to promote technological innovation in biomass utilization systems in Japanese rural areas based on widely abundant Japanese cedar (sugi) biomass. In this study, the process was evaluated by investigating the effects of the source sugi wood meal size and the solvent PEG molecular mass on the yield, chemical structure, molecular mass, and thermal properties of the resultant PEG-modified lignin derivatives, glycol lignins (GLs). Reducing the source wood meal size and PEG solvent molecular mass not only promoted lignin PEGylation but also the subsequent acid-induced chemical rearrangements of the GLs as demonstrated by chemical analyses, 2D NMR, and size exclusion chromatography (SEC). Reducing the source wood meal size and/or increasing the solvent PEG molecular mass enhanced the thermal properties of GLs as determined by thermomechanical analysis (TMA) and thermogravimetric analysis (TGA). We considered that the proposed process can efficiently produce lignin derivatives with substantial control over the chemical structure and thermal properties to meet commercial and industrial needs for lignin-based advanced material production.