Controlled Encapsulation of Gold Nanoparticles into Zr-Metal-Organic Frameworks with Improved Detection Limitation of Volatile Organic Compounds via Surface-Enhanced Raman Scattering.

Volatile organic compounds (VOCs) have harmful effects on human health and the environment but detecting low levels of VOCs is challenging due to a lack of reliable biomarkers. However, incorporating gold nanoparticles (Au NPs) into metal-organic frameworks (MOFs) shows promise for VOC detection. In this study, we developed nanoscale Au@UiO-66 that exhibited surface-enhanced Raman scattering (SERS) activity even at very low levels of toluene vapors (down to 1.0 ppm) due to the thickness of the shell and strong π-π interactions between benzenyl-type linkers and toluene. The UiO-66 shell also increased the thermal stability of the Au NPs, preventing aggregation up to 550 °C. This development may be useful for sensitive detection of VOCs for environmental protection purposes.

Thermochemical Conversion of Plastic Waste into Fuels, Chemicals, and Value-Added Materials: A Critical Review and Outlooks.

Plastic waste is an emerging environmental issue for our society. Critical action to tackle this problem is to upcycle plastic waste as valuable feedstock. Thermochemical conversion of plastic waste has received growing attention. Although thermochemical conversion is promising for handling mixed plastic waste, it typically occurs at high temperatures (300-800 °C). Catalysts can play a critical role in improving the energy efficiency of thermochemical conversion, promoting targeted reactions, and improving product selectivity. This Review aims to summarize the state-of-the-art of catalytic thermochemical conversions of various types of plastic waste. First, general trends and recent development of catalytic thermochemical conversions including pyrolysis, gasification, hydrothermal processes, and chemolysis of plastic waste into fuels, chemicals, and value-added materials were reviewed. Second, the status quo for the commercial implementation of thermochemical conversion of plastic waste was summarized. Finally, the current challenges and future perspectives of catalytic thermochemical conversion of plastic waste including the design of sustainable and robust catalysts were discussed.

Reaction Kinetics Regulated Formation of Short-Range Order in an Amorphous Matrix during Zeolite Crystallization.

The crystallization of zeolites, a disorder-to-order transformation of aluminosilicates, has not been thoroughly understood because the nucleation events in the amorphous matrix are difficult to recognize from the diverse structural changes, especially for the dense hydrogel systems. Therefore, relationships between the synthesis conditions, the generated amorphous species, and the crystallization behavior of zeolites remain unclear. Herein, by comparatively investigating the structural evolution of the aluminosilicate matrix in a dense hydrogel system when different Si reactants (fumed silica and silicate solution) are employed, we demonstrate that the reactivity of the reactants and the kinetics of the condensation reaction is critical to the formation of short-range order in an amorphous matrix, which greatly influences the nucleation frequency of zeolites. It was revealed that an amorphous solid containing plentiful Al-rich four-membered rings and Si-rich six-membered rings could be produced when fumed silica gradually reacted with sodium aluminate solution at 80 °C. It is considered that the interaction between these rings promotes the construction of the essential building units of zeolite X (FAU). In contrast, a complex aluminosilicate matrix was formed immediately when sodium silicate solution was mixed with sodium aluminate solution due to the intense condensation reaction. Furthermore, this complex matrix became more stable when the reactant mixture was hydrothermally treated at 80 °C, which significantly impedes the crystallization process. Aging the reactant mixture at ambient temperature before heating, instead, facilitated the formation of short-range order in the amorphous matrix, which increases the nucleation frequency of zeolites.

Rapid Fabrication of Biocomposites by Encapsulating Enzymes into Zn-MOF-74 via a Mild Water-Based Approach.

A zinc-based metal organic framework, Zn-MOF-74, which has a unique one-dimensional (1D) channel and nanoscale aperture size, was rapidly obtained in 10 min using a de novo mild water-based system at room temperature, which is an example of green and sustainable chemistry. First, catalase (CAT) enzyme was encapsulated into Zn-MOF-74 (denoted as CAT@Zn-MOF-74), and comparative assays of biocatalysis, size-selective protection, and framework-confined effects were investigated. Electron microscopy and powder X-ray diffraction were used for characterization, while electrophoresis and confocal microscopy confirmed the immobilization of CAT molecules inside the single hexagonal MOF crystals at loading of ∼15 wt %. Furthermore, the CAT@Zn-MOF-74 hybrid was exposed to a denaturing reagent (urea) and proteolytic conditions (proteinase K) to evaluate its efficacy. The encapsulated CAT maintained its catalytic activity in the decomposition of hydrogen peroxide (H2O2), even when exposed to 0.05 M urea and proteinase K, yielding an apparent observed rate constant (kobs) of 6.0 × 10-2 and 6.6 × 10-2 s-1, respectively. In contrast, free CAT exhibited sharply decreased activity under these conditions. Additionally, the bioactivity of CAT@Zn-MOF-74 for H2O2 decomposition was over three times better than that of the biocomposites based on zeolitic imidazolate framework 90 (ZIF-90) owing to the nanometer-scaled apertures, 1D channel, and less confinement effects in Zn-MOF-74 crystallites. To demonstrate the general applicability of this strategy, another enzyme, α-chymotrypsin (CHT), was also encapsulated in Zn-MOF-74 (denoted as CHT@Zn-MOF-74) for action against a substrate larger than H2O2. In particular, CHT@Zn-MOF-74 demonstrated a biological function in the hydrolysis of l-phenylalanine p-nitroanilide (HPNA), the activity of ZIF-90-encapsulated CHT was undetectable due to aperture size limitations. Thus, we not only present a rapid eco-friendly approach for Zn-MOF-74 synthesis but also demonstrate the broader feasibility of enzyme encapsulation in MOFs, which may help to meet the increasing demand for their industrial applications.

Synthetic and natural MOR zeolites as high-capacity adsorbents for the removal of nitrous oxide.

N2O is typically present as a trace gas in chemical processes, but its emission causes serious environmental issues. We herein demonstrate that ion-exchanged mordenite zeolites (framework code: MOR) can exhibit high capacities for N2O adsorption under ambient conditions. In particular, a natural MOR zeolite gives an adsorption capacity as high as 0.34 mmol-N2O per g-zeolite (1 atm, 25 °C), representing the best performing material among all zeolite-based adsorbents reported so far. The results contribute toward a comprehensive understanding of the structure-activity relationship and offer insights to establishing a zeolite-based adsorption system for enriching or removing N2O.

Functionalized Fe3O4@silica core-shell nanoparticles as microalgae harvester and catalyst for biodiesel production.

Core-shell Fe3O4@silica magnetic nanoparticles functionalized with a strong base, triazabicyclodecene (TBD), were successfully synthesized for harvesting microalgae and for one-pot microalgae-to-fatty acid methyl ester (FAME, or so-called biodiesel) conversion. Three types of algae oil sources (i.e., dried algae, algae oil, and algae concentrate) were used and the reaction conditions were optimized to achieve the maximum biodiesel yield. The results obtained in this study show that our TBD-functionalized Fe3O4@silica nanoparticles could effectively convert algae oil to biodiesel with a maximum yield of 97.1 %. Additionally, TBD-Fe3O4@silica nanoparticles act as an efficient algae harvester because of their adsorption and magnetic properties. The method presented in this study demonstrates the wide scope for the use of covalently functionalized core-shell nanoparticles for the production of liquid transportation fuels from algal biomass.