Valorizing natural-abundant glucose to lactic acid using a MOF-808 catalyst under green hydrothermal conditions.

Highly robust Zr-based MOF-808, featuring Lewis acid Zr sites and coordinate hydroxide ions upon the removal of the monocarboxylate capping reagent, emerges as an efficient catalyst for the hydrothermal conversion of glucose into lactic acid. A remarkable 99% glucose conversion with an impressive 76.6% yield of lactic acid can be achieved. The large pore window of MOF-808 facilitates the diffusion of glucose to the active sites within the framework. The single-site attribute of the catalytic center enables a high selectivity of lactic acid over the competitive product, 5-(hydroxymethyl)furfural, under hydrothermal reaction conditions.

Harvesting marine microalgae Tetraselmis sp. using cellulose acetate membrane.

This study presents the development and application of a cellulose acetate phase-inversion membrane for the efficient harvesting of Tetraselmis sp., a promising alternative for aquaculture feedstock. Once fabricated, the cellulose acetate membrane was characterized, and its performance was evaluated through the filtration of Tetraselmis sp. broth. The results demonstrated that the developed membrane exhibited exceptional microalgae harvesting efficiency. It showed a low intrinsic resistance and a high clean water permeability of 1100 L/(m2·h·bar), enabling high-throughput filtration of Tetraselmis sp. culture with a permeability of 400 L/(m2·h·bar) and a volume reduction factor of 2.5 ×. The cellulose acetate -based membrane demonstrated robust filtration performance over a 7-day back concentration filtration with minimum irreversible fouling of only 22.5 % irreversibility even without any cleaning. These results highlighted the potential of cellulose acetate as a versatile base polymer for custom-membrane for microalgae harvesting.

Unraveling Structural and Acidic Properties of Al-SBA-15-supported Metal Phosphates: Assessment for Glucose Dehydration.

5-Hydroxymethylfurfural (5-HMF) synthesized through glucose conversion requires Lewis acid (L) site for isomerization and Brønsted acid (B) site for dehydration. The objective of this work is to investigate the influence of the metal type of Al-SBA-15-supported phosphates of Cr, Zr, Nb, Sr, and Sn on glucose conversion to 5-HMF in a NaCl-H2 O/n-butanol biphasic solvent system. The structural and acid property of all supported metal phosphate samples were fully verified by several spectroscopic methods. Among those catalysts, CrPO/Al-SBA-15 provided the best performance with the highest glucose conversion and 5-HMF yield, corresponding to the highest total acidity of 0.65 mmol/g and optimal L/B ratio of 1.88. For CrPO/Al-SBA-15, another critical parameter is the phosphate-to-chromium ratio. Moreover, DFT simulation of glucose conversion to 5-HMF on the surface of the optimized chromium phosphate structure reveals three steps of fructose dehydration on the Brønsted acid site. Finally, the optimum reaction condition, reusability, and leaching test of the best catalyst were determined. CrPO/Al-SBA-15 is a promising catalyst for glucose conversion to high-value-added chemicals in future biorefinery production.

Solid-state mechanochemical synthesis of chitosan from mud crab (Scylla serrata) chitin.

This study presents a method for solvent-free mechanochemical synthesis of chitosan from chitin, sourced from the shells of mud crabs (Scylla serrata). The procedure involves a sequence of demineralization and deproteinization to extract chitin from the crab shells, followed by mechanochemical deacetylation. The chitin was deacetylated by grinding it as a solid blend with sodium hydroxide (NaOH) using a stainless steel mortar and pestle. After grinding, chitosan is isolated from the blend by repetitive washing and centrifugation. The chitosan product is then characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction analysis. These characterization techniques confirm the successful deacetylation of chitin to form chitosan. A high degree of deacetylation (DD) is achieved when the weight ratio of NaOH to chitin is 1:1 or higher, implying that the DD value can be enhanced by increasing this weight ratio. The mechanochemical reaction mechanism involves the hydroxyl groups on the NaOH particles reacting with the acetamide groups of the chitin strands, yielding solid chitosan and sodium acetate. This mechanochemical deacetylation approach is more practical than the conventional heterogeneous deacetylation in strong basic solutions, since it could suppress depolymerization of the resulting chitosan and requires significantly less base. This makes it a promising method for large-scale industrial applications.

Identification of Cooperative Reaction Sites in Metal-Organic Framework Catalysts for High Yielding Lactic Acid Production from d-Xylose.

Determining the roles of surface functionality of heterogeneous acid catalysts is important for many industrial catalysts. In this study, the decisive structure of metal-organic frameworks (MOFs) is utilized to identify important features for the effective conversion of d-xylose into lactic acid. Several acidic MOFs are tested and the combination of Lewis acidity and adjacent hydroxy sites is found to be critical to attain high lactic acid yields. This hypothesis is corroborated experimentally by modification of the MOF to increase such sites, which affords an enhanced lactic acid yield of 79 %, and investigation of the acidity by using in situ FTIR spectroscopy. Density functional theory calculations disclose the cooperative behavior of Lewis acid sites and hydroxy groups in promoting the Cannizzaro reaction, a key step in the production of lactic acid.

Engineering zirconium-based UiO-66 for effective chemical conversion of d-xylose to lactic acid in aqueous condition.

Utilizing metal-organic frameworks (MOFs) as heterogeneous catalysts is an interesting and important application due to their well-controlled catalytic sites and well-defined porous structures. In this study we apply, for the first time, Zr-based UiO-66 for the catalytic hydrothermal conversion of d-xylose to lactic acid (LA). The reactions are catalyzed by the coordinatively unsaturated Zr4+, as Lewis acid sites, and the hydroxide ion (OH-) located at the defect sites. The catalytic performances of UiO-66 catalysts synthesized through a modulator-free approach (UiO-66) and an acetic acid modulator-assisted approach (UiO-66(AA)) are distinct due to the different concentrations of local defects. The UiO-66 catalyst possessing a higher defect concentration exhibits a superior LA yield of 1.17 mol from 1 mol of xylose. However, the UiO-66(AA) catalyst with higher crystallinity shows better selectivity for LA over furfural, a side product from the competitive pathway. The enhanced LA yield and excellent selectivity can be achieved by the removal of AA from UiO-66(AA) resulting in a novel MOF catalyst (UiO-66(AA)*) which provides more accessible catalytic sites with retained crystallinity. This work highlights that the structural engineering of MOF catalysts is crucial for the fine-tuning of their catalytic properties.

Unsaturated Mn(II)-Centered [Mn(BDC)] n Metal-Organic Framework with Strong Water Binding Ability and Its Potential for Dehydration of an Ethanol/Water Mixture.

An unsaturated Mn(II)-centered metal-organic framework was synthesized. The presence of an unsaturated Mn(II) center, together with a guest-responsive structural changing feature, plays a crucial role for strong binding with water, leading to its potential application for water/ethanol separation. In addition, the present framework is thermally stable up to 400 °C, which is beneficial for the regeneration process after adsorption.