In this work, yellow pine (YP, softwood) and switchgrass (SG, grass) lignins were extracted as a coproduct of an organosolv γ-valerolactone (GVL) biorefinery that also produces biofuels and furfural. The extracted lignins were converted to carbon precursors for synthesizing porous activated carbon electrodes for high energy-density supercapacitors. This research details the impact of lignin composition on the derived porous structures and electrochemical properties of activated carbons. Lignin precursors with various syringyl (S) to guaiacyl (G) contents were characterized using 31P nuclear magnetic resonance (NMR) and two-dimensional 1H‒13C NMR. A two-step activation process, using steam and carbon dioxide as the activating agents, enabled the formation of porous carbons structures with high surface area. The capacitive behavior of supercapacitors was systematically characterized by cyclic voltammetry, charge-discharge cycling, and electrochemical impedance spectroscopy. The specific capacitance of YP and SG capacitors reached 367 and 221 F g−1, respectively. Both types of capacitors demonstrated remarkably stable capacitance (capacitance retention >90%) along with excellent Coulombic efficiency (>99%) over 10,000 cycles. Compared to SG electrode, the better electrochemical performance achieved with YP electrodes was mainly due to shorter diffusion path, improved ionic mobility, and increased active surface area. The inexpensive lignin-based porous electrodes synthesized in this work can be used for various electrochemical devices for improved performance, decreased cost, and enhanced durability. This work also demonstrates that the selection of feedstock and appropriate processing conditions can tailor the structure of carbon composites for targeted applications. Techno-economic analysis indicates that YP and SG activated carbons can be produced at a minimum selling price of $8,493 and $6,670 per ton, respectively, which is competitive with the commercially available supercapacitor-grade activated carbons.
Methyl bromide (MB) fumigation of oak (Quercus sp.) logs destined for export is required to mitigate risks associated with movement of the oak wilt fungus, Bretziella fagacearum. Alternative fumigants with efficacy against B. fagacearum are needed because of MB's ozone-depleting properties. Fumigation with sulfuryl fluoride (SF) is considered a promising substitute. Logs (1.8 m long) were obtained from Quercus trees (18.3 to 29.2 cm diameter at breast height) that were naturally infested (NI) or artificially inoculated (AI) with B. fagacearum to compare pathogen colonization and survival following fumigation with SF and MB. The logs were fumigated with SF for 72 hours with 240, 280, and 320 g/m3 or 96 hours with 128 and 240 g/m3. MB fumigations were conducted using the current treatment schedule for oak logs destined for export (240 g/m3 for 72 h). Frequencies of successful pathogen isolation before treatment were higher for AI logs than for NI logs based on isolation rates from sapwood chips. Treatments greatly reduced frequencies of viable pathogen presence, but no treatment was successful in eradicating the pathogen. Experiments were conducted on blocks (10.2 by 10.2 by 11.4 cm3) obtained from Quercus trees to investigate simulated penetration and diffusion of SF and MB into oak logs. Slow, variable fumigant diffusion never reached concentration–time products lethal to B. fagacearum. Based on these results, reliance on SF alone as a quarantine measure may require higher concentration × time products to achieve quarantine level control of the oak wilt fungus in logs.
Phytosanitary treatments for logs and barked wood products are needed to mitigate the spread of thousand cankers disease through the movement of these commodities. The disease threatens eastern black walnut (Juglans nigra L.) populations in the United States. It is caused by repeated attacks by the walnut twig beetle (Pityophthorus juglandis Blackman) and subsequent canker development caused by the fungal pathogen Geosmithia morbida M. Kolařík et al. Methyl bromide (MB) fumigations were evaluated for efficacy against P. juglandis and G. morbida in J. nigra bolts. Fumigation with 82 mg/L MB for 24 h at 4.5° C eliminated P. juglandis in J. nigra, but was ineffective against G. morbida. Subsequent experiments focused on eliminating G. morbida, but results were inconclusive because of low rates of pathogen recovery from naturally infested control bolts. Final experiments used J. nigra bolts artificially inoculated with G. morbida. Fumigations with 240 and 320 mg/L MB for 72 h at 10° C were effective in eliminating G. morbida from J. nigra bolts. Results confirm that the USDA fumigation treatment schedule for logs with the oak wilt pathogen will also mitigate the risk of spreading the thousand cankers disease vector and pathogen by movement of walnut bolts and wood products.
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