Nature-inspired optimization of hierarchical porous media for catalytic and separation processes

Hierarchical materials combining pore sizes of different length scales are highly important for catalysis and separation processes, where optimization of adsorption and transport properties is required. Nature can be an excellent guide to rational design, as it is full of hierarchical structures that are intrinsically scaling, efficient and robust. However, much of the “inspiration” from nature is, at present, empirical; considering the huge design space, we advocate a methodical, fundamental approach based on mechanistic features

Mesostructure of Mesoporous Silica/Anodic Alumina Hierarchical Membranes Tuned with Ethanol

Hierarchically structured membranes composed of mesoporous silica embedded inside the channels of anodic alumina (MS-AAM) were synthesized using the aspiration method. Ethanol is shown to have a significant effect on the type and organization of the mesoporous silica phase. Detailed textural analysis revealed that the pore size distribution of the mesoporous silica narrows and the degree of ordering increases with decreasing ethanol concentration used in the synthesis mixture. The silica mesopores were synthesized with pores as small as 6 nm in diameter, with the channel direction oriented in lamellar, circular, and columnar directions depending on the ethanol content. This study reveals ethanol concentration as a key factor behind the synthesis of an ordered mesoporous silica-anodic alumina membrane that can increase its functionality for membrane-based applications

Effect of stirring rate on the morphology of FDU-12 mesoporous silica particles

Ordered mesoporous FDU-12 silica particles with different morphologies were synthesized by varying the stirring rate. The mesoporous structure and textural properties of the FDU-12 samples were characterized by N2 adsorption and desorption, scanning electron microscopy, transmission electron microscopy and small angle X-ray scattering. The influence of the stirring conditions on the morphology was demonstrated, as the FDU-12 particle morphology changes from a regular, hexagonal platelet to a poorly defined shape when the stirring rate is changed from slow to fast. At very fast stirring rate, shear influences the mesophase structure, although the pore diameter and wall thickness remain unchanged

Chaperonin-Inspired pH Protection by Mesoporous Silica SBA-15 on Myoglobin and Lysozyme

While enzymes are valuable tools in many fields of biotechnology, they are fragile and must be protected against denaturing conditions such as unfavorable solution pH. Within living organisms, chaperonins help enzymes fold into their native shape and protect them from damage. Inspired by this natural solution, mesoporous silica SBA-15 with different pore diameters is synthesized as a support material for immobilizing and protecting enzymes. In separate experiments, the model enzymes myoglobin and lysozyme are physically adsorbed to SBA-15 and exposed to a range of buffered pH conditions. The immobilized enzymes' biocatalytic activities are quantified and compared to the activities of nonimmobilized enzymes in the same solution conditions. It has been observed that myoglobin immobilized on SBA-15 is protected from acidic denaturation from pH 3.6 to 5.1, exhibiting relative activity of up to 350%. Immobilized lysozyme is protected from unfavorable conditions from pH 6.6 to 7.6, with relative activity of up to 200%. These results indicate that the protective effects conferred to enzymes immobilized by physical adsorption to SBA-15 are driven by the enzymes' electrostatic attraction to the material's surface. The pore diameter of SBA-15 affects the quality of protection given to immobilized enzymes, but the contribution of this effect at different pH values remains unclear

Precisely Engineered Supported Gold Clusters as a Stable Catalyst for Propylene Epoxidation

Designing a stable and selective catalyst with high H2 utilisation is of pivotal importance for the direct gas-phase epoxidation of propylene. This work describes a facile one-pot methodology to synthesise ligand-stabilised sub-nanometre gold clusters immobilised onto a zeolitic support (TS-1) to engineer a stable Au/TS-1 catalyst. A non-thermal O2 plasma technique is used for the quick removal of ligands with limited increase in particle size. Compared to untreated Au/TS-1 catalysts prepared using the deposition precipitation method, the synthesised catalyst exhibits improved catalytic performance, including 10 times longer lifetime (>20 days), increased PO selectivity and hydrogen efficiency in direct gas phase epoxidation. The structure-stability relationship of the catalyst is illustrated using multiple characterisation techniques, such as XPS, 31P MAS NMR, DR-UV/VIS, HRTEM and TGA. It is hypothesised that the ligands play a guardian role in stabilising the Au particle size, which is vital in this reaction. This strategy is a promising approach towards designing a more stable heterogeneous catalyst

Gold nanoparticles with tailored size through ligand modification for catalytic applications

The active sites of catalysts can be tuned by using appropriate organic moieties. Here, we describe a facile approach to synthesise gold nanoparticles (AuNPs) using various Au(I) precursors. The core size of these AuNPs can be precisely tailored by varying the steric hindrance imposed by bound ligands. An interesting relationship is deduced that correlates the steric hindrance around the metal to the final size of the nanoparticles. The synthesised AuNPs are immobilised onto TS-1 zeolite (Au/TS-1) with minimal change in the final size of the AuNPs. The catalytic performance of Au/TS-1 catalyst is evaluated for the direct gas phase epoxidation of propylene with hydrogen and oxygen, an environmentally friendly route to produce propylene oxide. The results indicate that smaller AuNPs exhibit enhanced catalytic activity and selectivity. Furthermore, this synthetic approach is beneficial when tailored synthesis of gold nanoparticles of specific sizes is required

Mesostructure of Mesoporous Silica/Anodic Alumina Hierarchical Membranes Tuned with Ethanol (vol 33, pg 4823, 2017)

Correction to “Mesostructure of Mesoporous Silica/Anodic Alumina Hierarchical Membranes Tuned with Ethanol