ABSTRACT
The research of new porous materials for applications in interfacial processes is key to addressing global energy and sustainability challenges. For example, porous materials can be used to store fuels such as hydrogen or methane or to separate chemical mixtures reducing the energy currently required by thermal separation processes. Their catalytic properties can be exploited to convert adsorbed molecules into valuable or less hazardous chemicals, thereby reducing energy consumption or pollutants emissions. Porous boron nitride (BN) has appeared as a promising material for applications in molecular separations, gas storage, and catalysis owing to its high surface area and thermal stability, as well as its tunable physical properties and chemistry. However, the production of porous BN is still limited to the laboratory scale, and its formation mechanism, as well as ways to control porosity and chemistry, are yet to be fully understood. In addition, studies have pointed toward the instability of porous BN materials when exposed to humidity, which could significantly impact performance in industrial applications. Studies on porous BN performance and recyclability when employed in adsorption, gas storage, and catalysis remain limited, despite encouraging preliminary studies. Moreover, porous BN powder must be shaped into macrostructures (e.g., pellets) to be used commercially. However, common methods to shape porous materials into macrostructures often cause a reduction in the surface area and/or mechanical strength. In recent years, research groups, including ours, have started addressing the challenges discussed above. Herein, we summarize our collective findings through a selection of key studies. First, we discuss the chemistry and structure of BN, clarifying confusion around terminology and discussing the hydrolytic instability of the material in relation to its structure and chemistry. We demonstrate a way to reduce the instability in water while still maintaining high specific surface area. We propose a mechanism for the formation of porous BN and discuss the effects of different synthesis parameters on the structure and chemistry of porous BN, therefore providing a way to tune its properties for selected applications. While the syntheses covered often lead to a powder product, we also present ways to shape porous BN powders into macrostructures while still maintaining high accessible surface area for interfacial processes. Finally, we evaluate porous BN performance for chemical separations, gas storage, and catalysis. While the above highlights key advances in the field, further work is needed to allow deployment of porous BN. Specifically, we suggest evaluating its hydrolytic stability, refining the ways to shape the material into stable and reproducible macrostructures, establishing clear design rules to produce BN with specific chemistry and porosity, and, finally, providing standardized test procedures to evaluate porous BN catalytic and sorptive properties to facilitate comparison.
ABSTRACT
Shaped adsorbents (e.g., pellets, extrudates) are typically employed in several gas separation and sensing applications. The performance of these adsorbents is dictated by two key factors, their adsorption equilibrium capacity and kinetics. Often, adsorption equilibrium and textural properties are reported for materials. Adsorption kinetics are seldom presented due to the challenges associated with measuring them. The overarching goal of this work is to develop an approach to characterize the adsorption properties of individual shaped adsorbents with less than 100 mg of material. To this aim, we have developed an experimental dynamic sorption setup and complemented it with mathematical models, to describe the mass transport in the system. We embed these models into a derivative-free optimizer to predict model parameters for adsorption equilibrium and kinetics. We evaluate and independently validate the performance of our approach on three adsorbents that exhibit differences in their chemistry, synthesis, formulation, and textural properties. Further, we test the robustness of our mathematical framework using a digital twin. We show that the framework can rapidly (i.e., in a few hours) and quantitatively characterize adsorption properties at a milligram scale, making it suitable for the screening of novel porous materials.
ABSTRACT
This work reports the novel application of an Fe-based 2D metal-organic framework (MOF), prepared with 2,2'-bipyridine-5,5'-dicarboxylate (bpydc) as organic linker, as highly active catalyst for heterogeneous photoelectro-Fenton (PEF) treatment of the lipid regulator bezafibrate in a model matrix and urban wastewater. Well-dispersed 2D structures were successfully synthesized and their morphological, physicochemical and photocatalytic properties were assessed. UV/Vis PEF using an IrO2/air-diffusion cell with an extremely low catalyst concentration (0.05 g L-1, tenfold lower than reported 3D MOFs) outperformed electro-oxidation with electrogenerated H2O2, electro-Fenton and visible-light PEF. Its excellent performance was explained by: (i) the enhanced mass transport of H2O2 (and organic molecules) at the 2D structure, providing active sites for heterogeneous Fenton's reaction and in-situ Fe(II) regeneration; (ii) the ability of photoinduced electrons to reduce H2O2 to â¢OH, and Fe(III) to Fe(II); and (iii) the enhanced charge transfer and excitation of Fe-O clusters, which increased the number of electron-hole pairs. LC-QToF-MS and GC-MS allowed the identification of 16 aromatic products of bezafibrate. The complete removal of four micropollutants mixed in urban wastewater at pH 7.4 revealed the great potential of (Fe-bpydc)-catalyzed PEF process.
