An aerosol flow reactor was used for the first time for high-throughput, high yield synthesis of spherical lignin particles with given inherent hydrophilicity, depending on the precursor biomolecule. In situ fractionation via Berner type impactor afforded populations with characteristic sizes ranging from ∼30 nm to 2 μm. The as-produced, dry lignin particles displayed excellent mechanical integrity, even after redispersion under high shear in either mineral oil or water. They were effective in the stabilization of oil-in-water (O/W) Pickering emulsions with tunable droplet size, depending on the dimension of the lignin particles used for emulsification. The emulsion stability correlated with particle concentration as well as the respective lignin type. For the O/W emulsions stabilized with the more hydrophilic lignin particles, negligible changes in phase separation via Ostwald ripening and coalescence were observed over a period of time of more than two months. Together with the fact that the lignin particle concentrations used in emulsification were as low as 0.1%, our results reveal a remarkable ability to endow emulsified systems with high colloidal stability. Overall, we offer a new, high-yield, scalable nanomanufacturing approach to producing dry spherical lignin particles with size control and high production capacity. A number of emerging applications for these organic particles can be envisioned and, as a proof-of-concept, we illustrate here surfactant-free emulsification.
Recent progress in advanced nanostructures synthesized from biomass resources for the oxygen reduction reaction (ORR) is reviewed. The ORR plays a significant role in the performance of numerous energy-conversion devices, including low-temperature hydrogen and alcohol fuel cells, microbial fuel cells, as well as metal-air batteries. The viability of such fuel cells is strongly related to the cost of the electrodes, especially the cathodic ORR electrocatalyst. Hence, inexpensive and abundant plant and animal biomass have become attractive options to obtain electrocatalysts upon conversion into active carbon. Bioresource selection and processing criteria are discussed in light of their influence on the physicochemical properties of the ORR nanostructures. The resulting electrocatalytic activity and durability are introduced and compared to those from conventional Pt/C-based electrocatalysts. These ORR catalysts are also active for oxygen or hydrogen evolution reactions.
Sugar‐based biorefineries have faced significant economic challenges. Biorefinery lignins are often classified as low‐value products (fuel or low‐cost chemical feedstock) mainly due to low lignin purities in the crude material. However, recent research has shown that biorefinery lignins have a great chance of being successfully used as high‐value products, which in turn should result in an economy renaissance of the whole biorefinery idea. This critical review summarizes recent developments from our groups, along with the state‐of‐the‐art in the valorization of technical lignins, with the focus on biorefinery lignins.
A beneficial synergistic effect of lignin and cellulose mixtures used in different applications (wood adhesives, carbon fiber and nanofibers, thermoplastics) has been demonstrated. This phenomenon causes crude biorefinery lignins, which contain a significant amount of residual crystalline cellulose, to perform superior to high‐purity lignins in certain applications. Where previously specific applications required high‐purity and/or functionalized lignins with narrow molecular weight distributions, simple green processes for upgrading crude biorefinery lignin are suggested here as an alternative. These approaches can be easily combined with lignin micro‐/nanoparticles (LMNP) production. The processes should also be cost‐efficient compared to traditional lignin modifications.
Biorefinery processes allow much greater flexibility in optimizing the lignin characteristics desirable for specific applications than traditional pulping processes. Such lignin engineering, at the same time, requires an efficient strategy capable of handling large datasets to find correlations between process variables, lignin structures and properties and finally their performance in different applications.
Outstanding
optical and mechanical properties can be obtained from
hierarchical assemblies of nanoparticles. Herein, the formation of
helically ordered, chiral nematic films obtained from aqueous suspensions
of cellulose nanocrystals (CNCs) were studied as a function of the
initial suspension state. Specifically, nanoparticle organization
and the structural colors displayed by the resultant dry films were
investigated as a function of the anisotropic volume fraction (AVF),
which depended on the initial CNC concentration and equilibration
time. The development of structural color and the extent of macroscopic
stratification were studied by optical and scanning electron microscopy
as well as UV–vis spectroscopy. Overall, suspensions above
the critical threshold required for formation of liquid crystals resulted
in CNC films assembled with longer ranged order, more homogeneous
pitches along the cross sections, and narrower specific absorption
bands. This effect was more pronounced for the suspensions that were
closer to equilibrium prior to drying. Thus, we show that high AVF
and more extensive phase separation in CNC suspensions resulted in
large, long-range ordered chiral nematic domains in dried films. Additionally,
the average CNC aspect ratio and size distribution in the two separated
phases were measured and correlated to the formation of structured
domains in the dried assemblies.
High
yield (>85%) and low-energy deconstruction of never-dried
residual marine biomass is proposed following partial deacetylation
and microfluidization. This process results in chitin nanofibrils
(nanochitin, NCh) of ultrahigh axial size (aspect ratios of up to
500), one of the largest for bioderived nanomaterials. The nanochitins
are colloidally stable in water (ζ-potential = +95 mV) and produce
highly entangled networks upon pH shift. Viscoelastic and strong hydrogels
are formed by ice templating upon freezing and thawing with simultaneous
cross-linking. Slow supercooling and ice nucleation at −20
°C make ice crystals grow slowly and exclude nanochitin and cross-linkers,
becoming spatially confined at the interface. At a nanochitin concentration
as low as 0.4 wt %, highly viscoelastic hydrogels are formed, with
a storage modulus of ∼16 kPa, at least an order of magnitude
larger compared to those measured for the strongest chitin-derived
hydrogels reported so far. Moreover, the water absorption capacity
of the hydrogels reaches a value of 466 g g
–1
. Lyophilization
is effective in producing cryogels with a density that can be tailored
in a wide range of values, from 0.89 to 10.83 mg·cm
–3
, and corresponding porosity, between 99.24 and 99.94%. Nitrogen
adsorption results indicate reversible adsorption and desorption cycles
of macroporous structures. A fast shape recovery is registered from
compressive stress–strain hysteresis loops. After 80% compressive
strain, the cryogels recovered fast and completely upon load release.
The extreme values in these and other physical properties have not
been achieved before for neither chitin nor nanocellulosic cryogels.
They are explained to be the result of (a) the ultrahigh axial ratio
of the fibrils and strong covalent interactions; (b) the avoidance
of drying before and during processing, a subtle but critical aspect
in nanomanufacturing with biobased materials; and (c) ice templating,
which makes the hydrogels and cryogels suitable for advanced biobased
materials.
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