With rapidly increased interests in biomass, diverse chemical and biological processes have been applied for biomass utilization. Fourier transform infrared (FTIR) analysis has been used for characterizing different types of biomass and their products, including natural and processed biomass. During biomass treatments, some solvents and/or catalysts can be retained and contaminate biomass. In addition, contaminants can be generated by the decomposition of biomass components. Herein, we report FTIR analyses of a series of contaminants, such as various solvents, chemicals, enzymes, and possibly formed degradation by-products in the biomass conversion process along with poplar biomass. This information helps to prevent misunderstanding the FTIR analysis results of the processed biomass.
Selective cleavage of C−C bonds can be a valuable tool for various applications including polymer degradation and biomass utilization. Performing chemical transformations involving C−C bond cleavage steps under mild conditions and ambient temperature remains challenging due to the high dissociation energies of the C−C bond. This fundamental challenge can be solved by coupling a dye-sensitized photoelectrochemical cell (DSPEC) system, that generally targets the water splitting reaction, with a hydrogen atom transfer (HAT) mediator (HAT-DSPEC). Here, we report the solar-driven selective cleavage of the C(aryl)− C(alkyl) σ-bond in lignin at ambient temperature using an HAT-DSPEC under redox-neutral conditions. The photocatalyst (bis-2,2′-bipyridine)(2,2′-bipyridine-4,4′-dicarboxylic acid)Ru(II) (RuC) adsorbed onto a TiO 2 nanorod array with the length of ∼1.6 μm and a rod diameter of 100 nm atop fluorine-doped tin oxide (FTO|TiO 2 NRAs|RuC) film was prepared and investigated with an HAT mediator, 4-acetamido 2,2,6,6tetramethylpiperidine-1-oxyl (ACT), in solution. Photophysical and electrochemical studies of RuC and ACT with a lignin model compound, 1-(4-hydroxy-3,5-dimethoxyphenyl)-2-(2-methoxyphenoxy) propane-1,3-diol (LMC) reveal that the metal-toligand charge transfer (MLCT) excited states from the RuC are efficiently quenched in the presence of ACT with LMC. The HAT-DSPEC photoanode, containing the surface-bound photocatalyst RuC at the photoanode with ACT and LMC in solution, sustained an excellent photocurrent density, significantly outperforming that with the photocatalyst RuC alone. Moreover, the chemoselective cleavage of the C(aryl)−C(alkyl) bond in the LMC at the ambient temperature was demonstrated in the HAT-DSPEC system with a remarkable photocatalytic turnover number (>3000) leading to excellent selectivity (>90%) of C−C bond cleavage under AM1.5G irradiation (1 sun, 100 mW cm −2 ). These results were obtained over short reaction times and mild, redox-neutral reaction conditions without the need for extended reaction time (e.g., >24 h) or high temperature that is typical of homogeneous catalytic systems. This is the first report to demonstrate that an HAT-DSPEC can serve as a viable method for performing visible-light-driven selective C−C bond cleavage at ambient temperature.
The development of an energy-efficient
fractionation process as
well as the preservation of the fractionated cellulose, hemicellulose
sugars, and lignin are the key to the valorization of lignocellulose.
This study presents a mild-condition fractionation process based on
a recyclable and bifunctional 4-chlorobenzenesulfonic acid (4-Cl-BSA).
The aqueous (e.g., 72%) 4-Cl-BSA solution near-completely fractionated
unmilled poplar chips at 50–80 °C for 18–180 min
and successively preserved the theoretical maximum yields and key
structures of the fractionated cellulose, lignin, and hemicellulose
sugars. Around 21.3–27.8% lignin was hydrotropically dissolved
at a mesoscale level through accumulation by and complexation with
4-Cl-BSA and its aggregates. The solubilized lignin preserved about
24.7–50.7% of the 61% β-O-4 linkages in the native lignin
and about 48.3–82% aromatic units uncondensed. About 72.2–78.7%
lignin was insolubilized and quickly deposited on the surfaces of
cellulose fibers. Remarkably, the deposited lignin preserved about
61.9–81.1% of the β-O-4 linkages in the native lignin
and about 78.2–86.2% aromatic units uncondensed. Hemicellulose
sugars and cellulose (millimeter-size, CrI: 71–75, DPv: 910–1022) had high purity and high quality. Compared to
the other selected aryl sulfonic acids whether they have or do not
have substituents (dichloro, bromo, hydroxyl, and methyl) and mineral
acids, 4-Cl-BSA performed better in fractionating unmilled poplar
chips and preserving the β-O-4 linkages and aromatic units of
lignin. The results indicate that both acidity and hydrophobicity
of aryl sulfonic acid greatly influence its fractionation and preservation
performances.
The development of green materials, especially the preparation of high-performance conductive hydrogels from biodegradable biomass materials, is of great importance and has received worldwide attention. As an aromatic polymer found in many natural biomass resources, lignin has the advantage of being renewable, biodegradable, non-toxic, widely available, and inexpensive. The unique physicochemical properties of lignin, such as the presence of hydroxyl, carboxyl, and sulfonate groups, make it promising for use in composite conductive hydrogels. In this review, the source, structure, and reaction characteristics of industrial lignin are provided. Description of the preparation method (physical and chemical strategies) of lignin-based conductive hydrogel is elaborated along with their several important properties, such as electrical conductivity, mechanical properties, and porous structure. Furthermore, we provide insights into the latest research advances in industrial lignin conductive hydrogels, including biosensors, strain sensors, flexible energy storage devices, and other emerging applications. Finally, the prospects and challenges for the development of lignin-conductive hydrogels are presented.
Hydrogels have great potential in flexible moisture-induced electricity generators (MEGs) due to their excellent water-capturing capability and ionic conductivity. However, conventional hydrogels face challenges in prolonged heating for preparation, the...
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