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At least 775 records · Page 43

Conduction Band Fine Structure in Colloidal HgTe Quantum Dots

HgTe colloidal quantum dots (QDs) are of interest because quantum confinement of semimetallic bulk HgTe allows one to synthetically control the bandgap throughout the infrared. Here, we synthesize highly monodisperse HgTe QDs and tune their doping both chemically and electrochemically. The monodispersity of the QDs was evaluated using small-angle X-ray scattering (SAXS) and suggests a diameter distribution of similar to 10% across multiple batches of different sizes. Electron-doped HgTe QDs display an intraband absorbance and bleaching of the first two excitonic features. We see splitting of the intraband peaks corresponding to electronic transitions from the occupied 1S e state to a series of nondegenerate 1P e states. Spectroelectrochemical studies reveal that the degree of splitting and relative intensity of the intraband features remain constant across doping levels up to two electrons per QD. Theoretical modeling suggests that the splitting of the 1P e level arises from spin-orbit coupling and reduced QD symmetry. As a result, the fine structure of the intraband transitions is observed in the ensemble studies due to the size uniformity of the as-synthesized QDs and strong spin-orbit coupling inherent to HgTe.

36 MATERIALS SCIENCE↗

Wear Mechanism Analysis of a New Rotary Shear Biomass Comminution System

A new biomass comminution system, Crumbler rotary shear, was developed to process fuel-grade biomass. The rotary shear is more efficient than the traditional hammer mill in comminuting high-moisture biomass and producing more uniform particles with minimal fines. However, the milling unit experiences significant wear in processing dirty woodchips. This study investigated the wear mechanisms of the rotary shear system based on analysis of the minerals carried by woodchips and characterization of actual worn components. Abrasive wear was found to be the dominant effect, and localized adhesive wear (material transfer), microfracture (chipping), and plastic deformation were additional effects. Connections have been made between the wear progression of key cutting components and the particle size change of biomass extrinsic minerals. On the basis of the wear mechanism understanding, mitigations based on advanced tool materials and optimized tool geometric designs are being developed for improving the tool life and cutting efficiency.

09 BIOMASS FUELS↗

Life-Cycle Assessment of Sustainable Aviation Fuel Derived from Paper Sludge

Converting waste paper sludge to sustainable aviation fuel (SAF) offers a circular economy strategy to decarbonize the aviation sector. Here, this study develops a life-cycle assessment (LCA) for converting high-ash paper sludge to SAF in the U.S. using a catalytic sugar upgrading system that consists of ash removal, enzymatic hydrolysis, dehydration, aldol condensation, and hydroprocessing. The LCA is coupled with a process simulation for an industrial-scale biorefinery based on experimental data. We quantified the carbon intensity as 35.7–41.8 gCO 2 eq MJ –1 SAF (–636 to –584 gCO 2 eq per dry kg paper sludge) with acetone as a solvent, renewable fuel, and biobased chemicals; this is further reduced to 5.1–11.1 gCO 2 eq MJ –1 (–925 to –873 gCO 2 eq per dry kg paper sludge) if ash is recycled and used for substituting cement. Converting 1 dry kg paper sludge to SAF with acetone, renewable fuel, and biobased chemicals (–925 to –584 gCO 2 eq) is more climate beneficial than landfilling without landfill gas recovery (791 gCO 2 eq) and with landfill gas recovery (–294 gCO 2 eq). More than 330 million gallons of SAF can be produced annually (>4 million dry t paper sludge/year in the U.S.), resulting in a reduction of 2–7 million tCO 2 eq.

09 BIOMASS FUELS↗

Feasibility of Algal Biochar, a Byproduct of Biofuel Production, as a Supplemental Cementitious Material

Algal biochar, as the solid residue of biofuel production from algal biomass, is reported to explore disposition options, aiming to lessen the liability or obstacles to biofuel production processes. However, landfills and open combustion lead to adverse environmental impacts. One way to add value to such wastes is to use them as admixtures in cementitious construction materials. This study aims to investigate the feasibility of algae-derived biochar as supplementary cementitious materials (SCM) at different water contents and mixture ratios. Algal biochar-cement composites were prepared with different algal biochar content as well as different water-to-cement (w/c) ratios, and the surface area, morphology, elemental, and mineralogical composition were characterized. To compensate for the high-water absorption of algal biochar, a small concentration of a superplasticizer was used since higher w/c ratios negatively impact strength. The mechanical performance of algal biochar-cement composites is compared with control composites using commercial silica fume as a typical commercial SCM. The findings suggest that algal biochar is a promising candidate to replace commercial SCM, like silica fume, since algal biochar-cement composites can reach comparable compressive strength and Young’s modulus to commercial pozzolan-cement materials with the same w/c ratio, though at later curing times, 33 days. Although the tensile strength of algal biochar-cement composites is statistically similar at 7 days, it is significantly lower at later curing times, and further investigation is required to improve this property. Algal biochar-based cement binders showed comparable embodied carbon to silica fume-based cement binders based on a cradle-to-gate lifecycle analysis. However, the ability of algal biochar to absorb large volumes of CO 2 over short periods of time, as measured in this study, makes this novel SCM an excellent alternative to reduce the embodied carbon of concrete structures cradle-to-grave at 1/10 of the cost. In conclusion, valorization of algae-derived solid waste provides great potential to reduce embodied carbon and brings credit to biofuel production and concrete-based construction.

algae-derived↗

Insights of Ethanol Organosolv Pretreatment on Lignin Properties of Broussonetia papyrifera

Here, delignification of Broussonetia papyrifera during ethanol organosolv pretreatment was studied. Milled wood lignin (MWL), the ethanol organosolv lignin recovered at 5 min (PL5), 10 min (PL10), and 60 min (PL60) during the pretreatment, and the residual lignin (RL60) after the pretreatment were characterized and compared. GPC results demonstrated that the weight-average molecular weights ( M w ) of the ethanol organosolv lignin fractions increased as the pretreatment time extended from 5 to 60 min. 31 P NMR analysis revealed that the content of aliphatic OH decreased in the following order: RL60 < PL60 < PL5 < PL10 < MWL. HSQC NMR results suggested that the contents of syringyl, guaiacyl, p-hydroxybenzoate unit, phenylcoumaran, and resinol in the solubilized lignin fractions were significantly changed during the pretreatment. In addition, a significant portion of β-O-4 interunit linkages of lignin was cleaved during the pretreatment, leading to the formation of stilbene structures in lignin samples such as PL60.

54 ENVIRONMENTAL SCIENCES↗

Time-Dependent CO[subscript 2] Sorption Hysteresis in a One-Dimensional Microporous Octahedral Molecular Sieve

The development of sorbents for next-generation CO{sub 2} mitigation technologies will require better understanding of CO{sub 2}/sorbent interactions. Among the sorbents under consideration are shape-selective microporous molecular sieves with hierarchical pore morphologies of reduced dimensionality. We have characterized the non-equilibrium CO{sub 2} sorption of OMS-2, a well-known one-dimensional microporous octahedral molecular sieve with manganese oxide framework. Remarkably, we find that the degree of CO{sub 2} sorption hysteresis increases when the gas/sorbent system is allowed to equilibrate for longer times at each pressure step. Density functional theory calculations indicate a 'gate-keeping' role of the cation in the tunnel, only allowing CO{sub 2} molecules to enter fully into the tunnel via a highly unstable transient state when CO{sub 2} loadings exceed 0.75 mmol/g. The energy barrier associated with the gate-keeping effect suggests an adsorption mechanism in which kinetic trapping of CO{sub 2} is responsible for the observed hysteretic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Actinide Separation Inspired by Self-Assembled Metal–Polyphenolic Nanocages

The separation of actinides has a vital place in nuclear fuel reprocessing, recovery of radionuclides, and remediation of environmental contamination. Here we propose a new paradigm of nanocluster-based actinide separation, namely, nanoextraction, that can achieve efficient sequestration of uranium in an unprecedented form of giant coordination nanocages using a cone-shaped macrocyclic pyrogallol[4]arene as the extractant. The U 24 -based hexameric pyrogallol[4]arene nanocages with distinctive [U 2 (PG) 2 ] binuclear units (PG = pyrogallol) that rapidly assembled in situ in monophasic solvent were identified by single-crystal X-ray diffraction, MALDI-TOF mass spectrometry, NMR spectroscopy, and small-angle X-ray and neutron scattering. Furthermore, comprehensive biphasic extraction studies showed that this novel separation strategy has enticing advantages such as fast kinetics, high efficiency, and good selectivity over lanthanides, thereby demonstrating its potential for efficient separation of actinide ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–Organic Framework Based Hydrogen-Bonding Nanotrap for Efficient Acetylene Storage and Separation

The removal of carbon dioxide (CO 2 ) from acetylene (C 2 H 2 ) is a critical industrial process for manufacturing high purity C 2 H 2 . However, it remains challenging to address the trade-off between adsorption capacity and selectivity, on account of their similar physical properties and molecular sizes. To overcome this difficulty, here we report a novel strategy involving the regulation of hydrogen-bonding nanotrap on the pore surface to promote the separation of C 2 H 2 /CO 2 mixtures, in three isostructural metal-organic frameworks (MOFs, named as MIL-160, CAU-10H, and CAU-23, respectively). Among them, MIL-160, which has abundant hydrogen-bonding acceptors as nanotraps, can selectively capture acetylene molecules and demonstrates ultra-high C 2 H 2 storage capacity (191 cm 3 g –1 , or 213 cm 3 cm –3 ) but much less CO 2 uptake (90 cm 3 g –1 ) under ambient conditions. The C 2 H 2 adsorption amount of MIL-160 is remarkably higher than the other two isostructural MOFs (86 cm 3 g –1 and 119 cm 3 g –1 for CAU-10H and CAU-23 respectively) under the same conditions. More importantly, both simulation and experimental breakthrough results show that MIL-160 sets a new benchmark for equimolar C 2 H 2 /CO 2 separation in terms of the separation potential (Δq break = 5.02 mol/kg) and C 2 H 2 productivity (6.8 mol/kg). In addition, in-situ FT-IR experiments combined with computational modeling further reveal that the unique host-guest multiple hydrogen-bonding interactions between the nanotrap and C 2 H 2 is the key factor for achieving extraordinary acetylene storage capacity and superior C 2 H 2 /CO 2 selectivity. Furthermore, this work provides a novel and powerful approach to address the trade-off of this extremely challenging gas separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Derivation and Decoration of Nets with Trigonal-Prismatic Nodes: A Unique Route to Reticular Synthesis of Metal–Organic Frameworks

Quests for advanced functionalities in metal–organic frameworks (MOFs) inevitably encounter increasing complexity in their tailored framework architectures, accompanied by heightened challenges with their geometric design. Herein, we demonstrate the feasibility of rationally exploiting topological prediction as a blueprint for predesigned MOFs. A new triangular frusta secondary building unit (SBU), {Zn 4 (tz) 3 }, was bridged by three TDC 2– fragments to initially form a trigonal prismatic node, {Zn 8 (tz) 6 (TDC) 3 } (Htz = 1 H -1,2,3-triazole and H 2 TDC = 2,5-thiophenedicarboxylic acid). Furthermore, the trigonal prism unit can be considered as a double SBU derived from triply bound triangular frusta. By considering theoretical derived nets for linking this trigonal-prismatic node with ditopic, tritopic, and tetratopic linkers, we have synthesized and characterized a new family of MOFs that adopt the decorated lon , jea , and xai nets, respectively. Pore sizes have also been successively increased within TPMOF- n family, which facilitates heterogeneous biomimetic catalysis with Fe–porphyrin-based TPMOF-7 as a catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗