Joanna C. Rooke

Hierarchically structured zeolites: synthesis, mass transport properties and applications

Zeolites with hierarchically porous structures have garnered much attention due to their highly attractive properties. Hierarchically structured zeolites integrate at least two levels of porosity and present the advantages associated with each level of porosity, from selectivity to mass transport. They are categorized into three distinctly different types according to their hierarchical porosities: mesostructured zeolites, macrostructured zeolites, and micro–meso–macroporous structured zeolites. Most importantly, hierarchically structured zeolites offer an effective solution to the mass transport problem associated with conventional zeolites in catalysed reactions because they combine the catalytic features of micropores and the improved accessibility and increased molecular transport related to the addition of several porosities within a single body. In recent years, many strategies have been successfully developed to synthesize hierarchically structured zeolitic materials. This feature article thoroughly summarizes recent developments that have been achieved in the field of hierarchically structured zeolites, with the main focus on the synthesis strategies that are available, with examples given from the literature. Available approaches are reviewed for the preparation of micro–mesoporous structured zeolites, micro–macroporous structured zeolites and micro–meso–macroporous structured zeolites. Furthermore, the enhanced mass transport properties of hierarchically structured zeolites, featuring additional larger pores in addition to the crystalline micropores, have also been described. The significant improvement in catalytic properties in a range of important reactions resulting from enhanced mass transport properties have also been discussed through several representative cases. It is the intent of this work to stimulate intuition into the optimal design of related hierarchically organized zeolites with desired characteristics.

Whole-cell based hybrid materials for green energy production, environmental remediation and smart cell-therapy

This critical review highlights the advances that have been made over recent years in the domain of whole-cell immobilisation and encapsulation for applications relating to the environment and human health, particularly focusing on examples of photosynthetic plant cells, bacteria and algae as well as animal cells. Evidence that encapsulated photosynthetic cells remain active in terms of CO(2) sequestration and biotransformation (solar driven conversion of CO(2) into biofuels, drugs, fine chemicals etc.), coupled with the most recent advances made in the field of cell therapy, reveals the need to develop novel devices based on the preservation of living cells within abiotic porous frameworks. This review shall corroborate this statement by selecting precise examples that unambiguously demonstrate the necessity and the benefits of such smart materials. As will be described, the handling and exploitation of photosynthetic cells are enhanced by entrapment or encapsulation since the cells are physically separated from the liquid medium, thereby facilitating the recovery of the metabolites produced. In the case of animal cells, their encapsulation within a matrix is essential in order to create a physical barrier that can protect the cells auto-immune defenders upon implantation into a living body. For these two research axes, the key parameters that have to be kept in mind when designing hybrid materials will be identified, concentrating on essential aspects such as biocompatibility, mechanical strength and controlled porosity (264 references).

Ultralong Cu(OH)2 and CuO nanowire bundles: PEG200-directed crystal growth for enhanced photocatalytic performance

Ultralong Cu(OH)(2) and CuO nanowire bundles with lengths ranging from tens to hundreds of micrometers have been selectively synthesized on a large scale by a facile solution-phase method, using PEG200 as growth-directing agent. The growth mechanisms were investigated by monitoring the nanowire evolution process. The results showed that under the action of PEG200 molecules, the Cu(OH)(2) and CuO nanowires were first formed through oriented attachment of colloidal particles, then through side self-assembly leading to nanowire bundles, and finally to CuO nanoleaves. PEG200 plays a critical role in the synthesis of nanowires as it not only prevents the random aggregation of colloidal particles toward CuO nanoleaves but also helps to orientate nanowire growth by the coalescence and alignment in one direction of the colloidal particles. The concentration of OH(-) in the reaction system is also important for nanowire growth. In the absence of PEG200, nanoleaves are formed by an Ostwald ripening process. The band-gap value estimated from a UV-Vis absorption spectrum of CuO nanowire bundles is 2.32 eV. The photodegradation of a model pollutant, rhodamine B, by CuO nanowires and nanoleaves was compared with commercial nanopowders, showing that the as-synthesized ultralong CuO polycrystalline nanowire bundles have an enhanced photocatalytic activity with 87% decomposition of rhodamine B after an 8-h reaction, which was much higher than that of single-crystal nanoleaves (61%) and commercial nanopowders (32%). The origin of the high photocatalytic activity of these new polycrystalline CuO nanowire bundles has been discussed. This present work reveals that the (002) crystallographic surface is more favorable for photocatalytic decomposition of organic compounds and that these ultralong CuO nanowire bundles are potential candidates for photocatalysts in wastewater treatment.

Gold catalysts in environmental remediation and water-gas shift technologies

This review presents studies and investigations of the use of gold catalysts in environmental applications, from the oxidation of CO and volatile organic compounds (VOCs) in environmental technologies to the production of hydrogen, a non-polluting energy source, in the water-gas shift (WGS) reaction. It summarizes a variety of results, from the discovery made by Haruta et al. about the catalytic behaviour of gold in CO oxidation, to the use of gold-based catalysts in environmental remediation, by the catalytic removal of different types of VOC using a wide variety of oxide supports and finally to the use of this highly active noble metal in WGS applications. It also discusses gold loading methods, comparing them in terms of simplicity, efficiency and the resultant particle size and dispersion of Au over various supports. The application of different types of supporting materials is also presented, with a critical discussion of the parameters affecting the choice and use of such materials, i.e. how the support interacts with gold particles and with pollutant molecules along with the advantages a support offers to VOC oxidation and WGS reactions. It ends by highlighting the potential of gold catalyts in the future.

Well-Organized Zeolite Nanocrystal Aggregates with Interconnected Hierarchically Micro-Meso-Macropore Systems Showing Enhanced Catalytic Performance

Preparation and characterization of well-organized zeolitic nanocrystal aggregates with an interconnected hierarchically micro-meso-macro porous system are described. Amorphous nanoparticles in bimodal aluminosilicates were directly transformed into highly crystalline nanosized zeolites, as well as acting as scaffold template. All pores on three length scales incorporated in one solid body are interconnected with each other. These zeolitic nanocrystal aggregates with hierarchically micro-meso-macroporous structure were thoroughly characterized. TEM images and (29)Si NMR spectra showed that the amorphous phase of the initial material had been completely replaced by nanocrystals to give a micro-meso-macroporous crystalline zeolitic structure. Catalytic testing demonstrated their superiority due to the highly active sites and the presence of interconnected micro-meso-macroporosity in the cracking of bulky 1,3,5-triisopropylbenzene (TIPB) compared to traditional zeolite catalysts. This synthesis strategy was extended to prepare various zeolitic nanocrystal aggregates (ZSM-5, Beta, TS-1, etc.) with well-organized hierarchical micro-meso-macroporous structures.

Noble‐Metal‐Based Catalysts Supported on Zeolites and Macro‐Mesoporous Metal Oxide Supports for the Total Oxidation of Volatile Organic Compounds

The use of porous materials to eliminate volatile organic compounds (VOCs) has proven very effective towards achieving sustainability and environmental protection goals. The activity of zeolites and macro-mesoporous metal-oxide supports in the total oxidation of VOCs has been investigated, with and without noble-metal deposition, to develop highly active catalyst systems where the formation of by-products was minimal. The first catalysts employed were zeolites, which offered a good activity in the oxidation of VOCs, but were rapidly deactivated by coke deposition. The effects of the acido-basicity and ionic exchange of these zeolites showed that a higher basicity was related to exchanged ions with lower electronegativities, resulting in better catalytic performances in the elimination of VOCs. Following on from this work, noble metals were deposited onto macro-mesoporous metal-oxide supports to form mono and bimetallic catalysts. These were then tested in the oxidation of toluene to study their catalytic performance and their deactivation process. PdAu/TiO(2) and PdAu/TiO(2) -ZrO(2) 80/20 catalysts demonstrated the best activity and life span in the oxidation of toluene and propene and offered the lowest temperatures for a 50 % conversion of VOCs and the lowest coke content after catalytic testing. Different characterization techniques were employed to explain the changes occurring in catalyst structure during the oxidation of toluene and propene.

Novel 3DOM BiVO4/TiO2 nanocomposites for highly enhanced photocatalytic activity

Novel 3DOM BiVO4/TiO2 nanocomposites with intimate contact were for the first time synthesized by a hydrothermal method in order to elucidate their visible-light-driven photocatalytic performances. BiVO4 nanoparticles and 3DOM TiO2 inverse opal were fabricated respectively. These materials were characterized by XRD, XPS, SEM, TEM, N2 adsorption–desorption and UV-vis diffuse (UV-vis) and photoluminescence spectroscopies. As references for comparison, a physical mixture of BiVO4 nanoparticles and 3DOM TiO2 inverse opal powder (0.08 : 1), and a BiVO4/P25 TiO2 (0.08 : 1) nanocomposite made also by the hydrothermal method were prepared. The photocatalytic performance of all the prepared materials was evaluated by the degradation of rhodamine B (RhB) as a model pollutant molecule under visible light irradiation. The highly ordered 3D macroporous inverse opal structure can provide more active surface areas and increased mass transfer because of its highly accessible 3D porosity. The results show that 3DOM BiVO4/TiO2 nanocomposites possess a highly prolonged lifetime and increased separation of visible light generated charges and extraordinarily high photocatalytic activity. Owing to the intimate contact between BiVO4 and large surface area 3DOM TiO2, the photogenerated high energy charges can be easily transferred from BiVO4 to the 3DOM TiO2 support. BiVO4 nanoparticles in the 3DOM TiO2 inverse opal structure act thus as a sensitizer to absorb visible light and to transfer efficiently high energy electrons to TiO2 to ensure long lifetime of the photogenerated charges and keep them well separated, owing to the direct bandgap of BiVO4 of 2.4 eV, favourably positioned band edges, very low recombination rate of electron–hole pairs and stability when coupled with photocatalysts, explaining the extraordinarily high photocatalytic performance of 3DOM BiVO4/TiO2 nanocomposites. It is found that larger the amount of BiVO4 in the nanocomposite, longer the duration of photogenerated charge separation and higher the photocatalytic activity. This work can shed light on the development of novel visible light responsive nanomaterials for efficient solar energy utilisation by the intimate combination of an inorganic light sensitizing nanoparticle with an inverse opal structure with high diffusion efficiency and high accessible surface area.

Energy from photobioreactors: Bioencapsulation of photosynthetically active molecules, organelles, and whole cells within biologically inert matrices

Photosynthesis is a highly efficient solar energy transformation process. Exploiting this natural phenomenon is one way to overcome the shortage in the Earth’s fuel resources. This review summarizes the work carried out in the field of photobioreactor design via the immobilization of photosynthetically active matter within biologically inert matrices and the potential biotechnological applications of the obtained hybrid materials within the domain of solar energy to chemical energy transformation. The first part deals with the design of artificial photosynthetic reaction centers (RCs) by the encapsulation of pigments, proteins, and complexes. The action of thylakoids, chloroplasts, and whole plant cells, immobilized in biocompatible supports, in the conversion of CO2 into chemical energy, is also addressed. Finally, the latest advances in the exploitation of the bioactivity of photosynthetically active micro-organisms are explored in terms of the production of secondary metabolites and hydrogen.

Synthesis and applications of hierarchically porous catalysts

Abstract Hierarchically porous materials that can be used as catalysts or catalyst supports have garnered much attention due to their enhanced mass transport and multiple functionalities. Hierarchically porous catalysts integrate at least two levels of porosity and present the advantages associated with each level of porosity, from selectivity to mass transport. For example, hierarchically porous zeolites offer an effective solution to the mass transport problem associated with conventional zeolites in catalyzed reactions, because they combine the catalytic features of micropores and the improved accessibility and increased molecular transport related to the addition of several porosities within a single body. This review thoroughly summarizes recent developments that have been made in the field of hierarchically porous catalysts, with the main focus on the synthesis strategies that are available as well as their application in catalysis. It is the intent of this work to stimulate intuition into the optimal design of related hierarchically porous catalysts with desired characteristics.

Biofuel cells Based on the Immobilization of Photosynthetically Active Bioentities

Natural photosynthesis is a highly efficient process that uses sunlight irradiation to convert carbon dioxide into value‐added biomass. This review summarizes the recent advances in the transformation of solar energy into electrical power through the exploitation of photosynthetically active proteins, organelles, and living cells. During the past decade, the considerable progress made in bioentities immobilization offers the possibility to integrate biological systems into electronic devices. Even though solar energy technologies are gaining increasing attention, photosynthetic biofuel cells are still in their infancy. Advances in materials science are necessary to protect, stabilize, and even increase the catalytic performance of bioentities. Moreover, host materials could guarantee higher loading and better electrical charge transport, which would be crucial in the commercial success of biofuel cells. In the future, such semi‐artificial hybrid assemblies could hold promise as sustainable sources of energy.