Development of TiO2-CaCO3 Based Composites as an Affordable Building Material for the Photocatalytic Abatement of Hazardous NOx from the Environment.

This study explores the depollution activity of a photocatalytic cementitious composite comprising various compositions of n-TiO2 and CaCO3. The photocatalytic activity of the CaCO3-TiO2 composite material is assessed for the aqueous photodegradation efficiency of MB dye solution and NOx under UV light exposure. The catalyst CaCO3-TiO2 exhibits the importance of an optimal balance between CaCO3 and n-TiO2 for the highest NOx removal of 60% and MB dye removal of 74.6%. The observed trends in the photodegradation of NOx removal efficiencies suggest a complex interplay between CaCO3 and TiO2 content in the CaCO3-n-TiO2 composite catalysts. This pollutant removal efficiency is attributed to the synergistic effect between CaCO3 and n-TiO2, where a higher percentage of n-TiO2 appeared to enhance the photocatalytic activity. It is recommended that CaCO3-TiO2 photocatalysts are effectiveness in water and air purification, as well as for being cost-effective construction materials.

Facile and Simple Post Treatment Ball Milling Strategy for the Production of Low-Cost TiO2 Composites with Enhanced Photocatalytic Performance and Applicability to Construction Materials.

A facile and cost-effective approach assisted by ball milling (BM) of commercial titanium dioxide (TiO2), has been utilized to develop cheaper and efficient construction materials. At least three of the commercial and cheaper TiO2 samples (BA01-01, BA01-01+ and R996, designated as A1, A4 and R1, respectively) were selected and subjected to BM treatment to enhance their photocatalytic efficiencies, if possible. It was noted, that the samples A1, A4 and R1 were typical composites of TiO2 and calcium carbonate (CaCO3) and contained varying proportions of anatase, and rutile phases of TiO2 and CaCO3. Two of the highly efficient commercial TiO2 samples, Degussa P25 (simply designated as P25) and ST01 (Ishihara Ind.) were selected for making benchmark comparisons of photocatalytic efficiencies. The BM treated TiO2 samples (designated as TiO2-BM with respect to A1, A4 and R1) were evaluated for photocatalytic efficiencies both in both aqueous (methylene blue (MB)) and gaseous (NOx) photodegradation reactions. Based on detailed comparative investigations, it was observed that A1-BM photocatalyst exhibited superior photocatalytic performances over A4-BM and R1-BM, towards both MB and NOx photodegradation reactions. The difference of NOx photodegradation efficiency between the mortar mixed with A1-BM and that mixed with ST01, and P-25 at 15% were 16.6%, and 32.4%, respectively. Even though the mortar mixed with A1-BM at 15% composition exhibited a slightly lower NOx photodegradation efficiency as compared to mortar mixed with the expensive ST01 and P-25 photocatalysts, the present work promises an economic application in the eco-friendly construction materials for air purification considering the far lower cost of A1. The reasons for the superior performance of A1-BM were deduced through characterization of optical properties, surface characteristics, phase composition, morphology, microstructure and particle size distribution between pristine and BM treated A1 using characterization techniques such as diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction analysis, field emission scanning electron microscopy and particle size analysis.

Tetrahedral atom ordering in a zeolite framework: a key factor affecting its physicochemical properties.

Three gallosilicate natrolites with closely similar chemical composition but differing in the distribution of Si and Ga over crystallographically different tetrahedral sites (T-sites) show striking differences in their cation exchange performance. The ability to exchange Na(+) by the larger alkali metal cations decreases upon increasing the size of the cation, as expected, but also with the degree of T-atom ordering. To seek an insight into this phenomenon, the crystal structures of 11 different zeolites, which show variations in degree of T-atom ordering, nature of countercation, and hydration state, have been refined using synchrotron diffraction data. While the three as-made sodium materials were characterized to have a low, medium, and high degree of ordering, respectively, their pore sizes are close to the size of the bare Na(+) cation and much smaller than that of the larger alkali cations, which are nonetheless exchanged into the materials, each one at a different level. Interestingly, large differences are also manifested when the Na(+) back-exchange is performed on the dehydrated K(+) forms, with crystallographic pore sizes too small even to allow the passage of Na(+). Although the thermodynamic data point to small differences in the enthalpy of the Na(+)/K(+) exchange in the three materials, comparison of the "static" crystallographic pore sizes and the diameter of the exchanged cations lead us to conclude that during the exchange process these zeolites undergo significant deformations that dynamically open the pores, allowing cation traffic even for Cs(+) in the case of the most disordered material. In addition to the very large topological flexibility typical of the natrolite framework, we propose as a hypothesis that there is an additional flexibility mechanism that decreases the rigidity of the natrolite chain itself and is dependent on preferential siting of Si or Ga on crystallographically different T-sites.

Facile Use of Silver Nanoparticles-Loaded Alumina/Silica in Nanofluid Formulations for Enhanced Catalytic Performance toward 4-Nitrophenol Reduction.

The introduction of toxic chemicals into the environment can result in water pollution leading to the degradation of biodiversity as well as human health. This study presents a new approach of using metal oxides (Al2O3 and SiO2) modified with a plasmonic metal (silver, Ag) nanoparticles (NPs)-based nanofluid (NF) formulation for environmental remediation purposes. Firstly, we prepared the Al2O3 and SiO2 NFs of different concentrations (0.2 to 2.0 weight %) by ultrasonic-assisted dispersion of Al2O3 and SiO2 NPs with water as the base fluid. The thermo-physical (viscosity, activation energy, and thermal conductivity), electrical (AC conductivity and dielectric constant) and physical (ultrasonic velocity, density, refractive index) and stability characteristics were comparatively evaluated. The Al2O3 and SiO2 NPs were then catalytically activated by loading silver NPs to obtain Al2O3/SiO2@Ag composite NPs. The catalytic reduction of 4-nitrophenol (4-NP) with Al2O3/SiO2@Ag based NFs was followed. The catalytic efficiency of Al2O3@Ag NF and SiO2@Ag NF, for the 4-NP catalysis, is compared. Based on the catalytic rate constant evaluation, the catalytic reduction efficiency for 4-NP is found to be superior for 2% weight Al2O3@Ag NF (92.9 × 10-3 s-1) as compared to the SiO2@Ag NF (29.3 × 10-3 s-1). Importantly, the enhanced catalytic efficiency of 2% weight Al2O3@Ag NF for 4-NP removal is much higher than other metal NPs based catalysts reported in the literature, signifying the importance of NF formulation-based catalysis.

Polyethylene Glycol Coated Magnetic Nanoparticles: Hybrid Nanofluid Formulation, Properties and Drug Delivery Prospects.

Magnetic nanoparticles (MNPs) are widely used materials for biomedical applications owing to their intriguing chemical, biological and magnetic properties. The evolution of MNP based biomedical applications (such as hyperthermia treatment and drug delivery) could be advanced using magnetic nanofluids (MNFs) designed with a biocompatible surface coating strategy. This study presents the first report on the drug loading/release capability of MNF formulated with methoxy polyethylene glycol (referred to as PEG) coated MNP in aqueous (phosphate buffer) fluid. We have selected MNPs (NiFe2O4, CoFe2O4 and Fe3O4) coated with PEG for MNF formulation and evaluated the loading/release efficacy of doxorubicin (DOX), an anticancer drug. We have presented in detail the drug loading capacity and the time-dependent cumulative drug release of DOX from PEG-coated MNPs based MNFs. Specifically, we have selected three different MNPs (NiFe2O4, CoFe2O4 and Fe3O4) coated with PEG for the MNFs and compared their variance in the loading/release efficacy of DOX, through experimental results fitting into mathematical models. DOX loading takes the order in the MNFs as CoFe2O4 > NiFe2O4 > Fe3O4. Various drug release models were suggested and evaluated for the individual MNP based NFs. While the non-Fickian diffusion (anomalous) model fits for DOX release from PEG coated CoFe2O4, PEG coated NiFe2O4 NF follows zero-order kinetics with a slow drug release rate of 1.33% of DOX per minute. On the other hand, PEG coated NiFe2O4 follows zero-order DOX release. Besides, several thermophysical properties and magnetic susceptibility of the MNFs of different concentrations have been studied by dispersing the MNPs (NiFe2O4, CoFe2O4 and Fe3O4) in the base fluid at 300 K under ultrasonication. This report on the DOX loading/release capability of MNF will set a new paradigm in view that MNF can resolve problems related to the self-heating of drug carriers during mild laser treatment with its thermal conducting properties.

Calcite-forming bacteria for compressive strength improvement in mortar.

Microbiological calcium carbonate precipitation (MCP) has been investigated for its ability to improve the compressive strength of concrete mortar. However, very few studies have been conducted on the use of calcite-forming bacteria (CFB) to improve compressive strength. In this study, we discovered new bacterial genera that are capable of improving the compressive strength of concrete mortar. We isolated 4 CFB from 7 environmental concrete structures. Using sequence analysis of the 16S rRNA genes, the CFB could be partially identified as Sporosarcina soli KNUC401, Bacillus massiliensis KNUC402, Arthrobacter crystallopoietes KNUC403, and Lysinibacillus fusiformis KNUC404. Crystal aggregates were apparent in the bacterial colonies grown on an agar medium. Stereomicroscopy, scanning electron microscopy, and x-ray diffraction analyses illustrated both the crystal growth and the crystalline structure of the CaCO3 crystals. We used the isolates to improve the compressive strength of concrete mortar cubes and found that KNUC403 offered the best improvement in compressive strength.

Manganese and Graphene Included Titanium Dioxide Composite Nanowires: Fabrication, Characterization and Enhanced Photocatalytic Activities.

We report the detailed microstructural, morphological, optical and photocatalytic studies of graphene (G) and manganese (Mn) co-doped titanium dioxide nanowires (TiO2(G-Mn) NWs) prepared through facile combined electrospinning-hydrothermal processes. The as-prepared samples were thoroughly characterized using X-ray diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and diffuse reflectance spectroscopy (DRS). XRD studies reveal the formation of mixed anatase-rutile phases or rutile phase depending on the dopant (Mn) precursor concentrations in the electrospinning dope and calcination temperature. The evaluation of lattice parameters revealed that the incorporation of Mn species and carbon atoms in to the lattice of anatase or rutile TiO2 could occur through substituting the sites of oxygen atoms. XPS results confirm the existence of Mn2+/Mn3+ within the TiO2 NW. Raman spectroscopy provides the evidence for structural modification because of the graphene inclusion in TiO2 NW. The optical band gap of G-Mn including TiO2 is much lower than pristine TiO2 as confirmed through UV-vis DRS. The photocatalytic activities were evaluated by nitric oxide (NOx) degradation tests under visible light irradiation. Superior catalytic activity was witnessed for rutile G-Mn-co-doped TiO2 NW over their anatase counterparts. The enhanced photocatalytic property was discussed based on the synergistic effects of doped G and Mn atoms and explained by plausible mechanisms.

Cost-Effective Production of TiO2 with 90-Fold Enhanced Photocatalytic Activity Via Facile Sequential Calcination and Ball Milling Post-Treatment Strategy.

Titanium dioxide (TiO2), the golden standard among the photocatalysts, exhibits a varying level of photocatalytic activities (PCA) amongst the synthetically prepared and commercially available products. For commercial applications, superior photoactivity and cost-effectiveness are the two main factors to be reckoned with. This study presents the development of simple, cost-effective post-treatment processes for a less costly TiO2 to significantly enhance the PCA to the level of expensive commercial TiO2 having demonstrated superior photoactivities. We have utilized sequential calcination and ball milling (BM) post-treatment processes on a less-costlier KA100 TiO2 and demonstrated multi-fold (nearly 90 times) enhancement in PCA. The post-treated KA100 samples along with reference commercial samples (P25, NP400, and ST01) were well-characterized by appropriate instrumentation and evaluated for the PCA considering acetaldehyde photodegradation as the model reaction. Lattice parameters, phase composition, crystallite size, surface functionalities, titanium, and oxygen electronic environments were evaluated. Among post-treated KA100, the sample that is subjected to sequential 700 °C calcination and BM (KA7-BM) processes exhibited 90-fold PCA enhancement over pristine KA100 and the PCA-like commercial NP400 (pure anatase-based TiO2). Based on our results, we attribute the superior PCA for KA7-BM due to the smaller crystallite size, the co-existence of mixed anatase-srilankite-rutile phases, and the consequent multiphase heterojunction formation, higher surface area, lattice disorder/strain generation, and surface oxygen environment. The present work demonstrates a feasible potential for the developed post-treatment strategy towards commercial prospects.

Recent Progress in the Abatement of Hazardous Pollutants Using Photocatalytic TiO2-Based Building Materials.

Titanium dioxide (TiO2) has been extensively investigated in interdisciplinary research (such as catalysis, energy, environment, health, etc.) owing to its attractive physico-chemical properties, abundant nature, chemical/environmental stability, low-cost manufacturing, low toxicity, etc. Over time, TiO2-incorporated building/construction materials have been utilized for mitigating potential problems related to the environment and human health issues. However, there are challenges with regards to photocatalytic efficiency improvements, lab to industrial scaling up, and commercial product production. Several innovative approaches/strategies have been evolved towards TiO2 modification with the focus of improving its photocatalytic efficiency. Taking these aspects into consideration, research has focused on the utilization of many of these advanced TiO2 materials towards the development of construction materials such as concrete, mortar, pavements, paints, etc. This topical review focuses explicitly on capturing and highlighting research advancements in the last five years (mainly) (2014-2019) on the utilization of various modified TiO2 materials for the development of practical photocatalytic building materials (PBM). We briefly summarize the prospective applications of TiO2-based building materials (cement, mortar, concretes, paints, coating, etc.) with relevance to the removal of outdoor/indoor NOx and volatile organic compounds, self-cleaning of the surfaces, etc. As a concluding remark, we outline the challenges and make recommendations for the future outlook of further investigations and developments in this prosperous area.

Nanophase Changes in Nickel Doped Titania Composites by Thermal Treatment and Photocatalytic Destruction of NO(x).

This study investigated the influence of Ni doping and thermal treatment (600, 800 degrees and 1000 degrees C) on the physiochemical properties of a commercially available low cost KA100 TiO2. Ni containing KA100 samples were prepared with different loading of Ni (3%, 6% and 9% wt to KA100) and subjected to heat treatement at 600 degrees, 800 degrees and 1000 degrees C. The as-prepared samples were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Diffuse reflection UV-Visible spectroscopy and Raman spectroscopy and nitrogen-adsorption-desorption measurements to observe the nanophase changes in the particle characteristics following Ni modification and thermal treatment. The results show that the Ni atom entered the TiO2 lattice structure upon heat treatment at 800 degrees C and 1000 degrees C influencing the anatase-rutile phase transformation. The TiO2 powders after heat treatment had a bimodal pore-size distribution as the temperature of the heat treatment increased. In addition, the anatase crystallite size and average pore sizes increased. Photodegradation of NO(x) was investigated using the Ni doped KA100 as a photocatalyst. Modification of KA100 with nickel and heat treatment up to 1000 degrees C enhanced the photocatalysis for the degradation of NO(x). Typically, KA100 modified with 6% Ni and heat treated to 1000 degrees C exhibited excellent NO(x) removal activity.

Effect of Microorganism Sporosarcina pasteurii on the Hydration of Cement Paste.

Years of research have shown that the application of microorganisms increases the compressive strength of cement-based material when it is cured in a culture medium. Because the compressive strength is strongly affected by the hydration of cement paste, this research aimed to investigate the role of the microorganism Sporosarcina pasteurii in hydration of cement paste. The microorganism's role was investigated with and without the presence of a urea-CaCl2 culture medium (i.e., without curing the specimens in the culture medium). The results showed that S. pasteurii accelerated the early hydration of cement paste. The addition of the urea-CaCl2 culture medium also increased the speed of hydration. However, no clear evidence of microbially induced calcite precipitation appeared when the microorganisms were directly mixed with cement paste.

Application of Bacillus subtilis 168 as a multifunctional agent for improvement of the durability of cement mortar.

Microbiological calcium carbonate precipitation (MCCP) has been investigated for its ability to improve the durability of cement mortar. However, very few strains have been applied to crack remediation and strengthening of cementitious materials. In this study, we report the biodeposition of Bacillus subtilis 168 and its ability to enhance the durability of cement material. B. subtilis 168 was applied to the surface of cement specimens. The results showed a new layer of deposited organic-inorganic composites on the surface of the cement paste. In addition, the water permeability of the cement paste treated with B. subtilis 168 was lower than that of non-treated specimens. Furthermore, artificial cracks in the cement paste were completely remediated by the biodeposition of B. subtilis 168. The compressive strength of cement mortar treated with B. subtilis 168 increased by about 19.5% when compared with samples completed with only B4 medium. Taken together, these findings suggest that the biodeposition of B. subtilis 168 could be used as a sealing and coating agent to improve the strength and water resistance of concrete. This is the first paper to report the application of Bacillus subtilis 168 for its ability to improve the durability of cement mortar through calcium carbonate precipitation.

Application of alkaliphilic biofilm-forming bacteria to improve compressive strength of cement-sand mortar.

The application of microorganisms in the field of construction material is rapidly increasing worldwide; however, almost all studies that were investigated were bacterial sources with mineral-producing activity and not with organic substances. The difference in the efficiency of using bacteria as an organic agent is that it could improve the durability of cement material. This study aimed to assess the use of biofilm-forming microorganisms as binding agents to increase the compressive strength of cement-sand material. We isolated 13 alkaliphilic biofilmforming bacteria (ABB) from a cement tetrapod block in the West Sea, Korea. Using 16S RNA sequence analysis, the ABB were partially identified as Bacillus algicola KNUC501 and Exiguobacterium marinum KNUC513. KNUC513 was selected for further study following analysis of pH and biofilm formation. Cement-sand mortar cubes containing KNUC513 exhibited greater compressive strength than mineral-forming bacteria (Sporosarcina pasteurii and Arthrobacter crystallopoietes KNUC403). To determine the biofilm effect, Dnase I was used to suppress the biofilm formation of KNUC513. Field emission scanning electron microscopy image revealed the direct involvement of organic-inorganic substance in cement-sand mortar.

Application of antifungal CFB to increase the durability of cement mortar.

Antifungal cement mortar or microbiological calcium carbonate precipitation on cement surface has been investigated as functional concrete research. However, these research concepts have never been fused with each other. In this study, we introduced the antifungal calciteforming bacteria (CFB) Bacillus aryabhattai KNUC205, isolated from an urban tunnel (Daegu, South Korea). The major fungal deteriogens in urban tunnel, Cladosporium sphaerospermum KNUC253, was used as a sensitive fungal strain. B. aryabhattai KNUC205 showed CaCO3 precipitation on B4 medium. Cracked cement mortar pastes were made and neutralized by modified methods. Subsequently, the mixture of B. aryabhattai KNUC205, conidiospore of C. sphaerospermum KNUC253, and B4 agar was applied to cement cracks and incubated at 18 degrees C for 16 days. B. aryabhattai KNUC205 showed fungal growth inhibition against C. sphaerospermum. Furthermore, B. aryabhattai KNUC205 showed crack remediation ability and water permeability reduction of cement mortar pastes. Taken together, these results suggest that the CaCO3 precipitation and antifungal properties of B. aryabhattai KNUC205 could be used as an effective sealing or coating material that can also prevent deteriorative fungal growth. This study is the first application and evaluation research that incorporates calcite formation with antifungal capabilities of microorganisms for an environment-friendly and more effective protection of cement materials. In this research, the conception of microbial construction materials was expanded.