Attachment Of Particles Research Articles

Formation Mechanism of Polypyrrole-Coated Hollow Glass Microspheres (PPy@HGMs) Composite Powder.

Coating conductive nanoparticles onto the surface of hollow glass microspheres (HGMs) is essential for broadening their applications. However, the low density and high specific surface area of HGM powders, along with the thin walls of the cavity shells and poor surface adhesion, pose challenges for the uniform attachment of functional particles. In this study, we developed a novel integrated process that combines flotation, hydroxylation, and amination pretreatment for HGMs with in situ surface polymerization to achieve a uniform coating of polypyrrole (PPy) on the surface of HGMs. We explored the corresponding growth process and coating mechanism. Our findings indicate that the amount of coating, particle size, and uniformity of PPy on the surface of HGMs are significantly influenced by the pretreatment and the in situ polymerization time, as well as the microspheres/pyrrole feedstock ratio. The in situ polymerization on the surface of HGMs resulted in a uniform encapsulation of spherical PPy, with the average particle size of PPy-coated HGMs (PPy@HGMs) increasing by 14.60% compared to the original HGMs. The elemental nitrogen in the PPy@HGMs primarily exists in the form of C-N and N-H bonds. This study demonstrates that the surface functional groups of HGMs engage in chemical bonding and interactions with PPy molecules. Mechanistic analysis reveals that the hydroxyl and amino groups enriched on the surface of the pretreated HGMs serve as activation centers, facilitating the uniform enrichment of pyrrole monomers and promoting chain growth polymerization of the conjugated chain through nucleophilic and electrophilic interactions with the subamino groups in the pyrrole ring. Additionally, the reaction between the Lewis acid properties of PPy and the Lewis-type electron-donating amino groups in KH550 fosters strong bonding and the formation of a robust interface.

Novel isolates expand the physiological diversity of Prochlorococcus and illuminate its macroevolution.

Prochlorococcus is a diverse picocyanobacterial genus and the most abundant phototroph on Earth. Its photosynthetic diversity divides it into high-light (HL)- or low-light (LL)-adapted groups representing broad phylogenetic grades-each composed of several monophyletic clades. Here, we physiologically characterize four new Prochlorococcus strains isolated from below the deep chlorophyll maximum in the North Pacific Ocean. We combine these physiological properties with genomic analyses to explore the evolution of photosynthetic antennae and discuss potential macroevolutionary implications. The isolates belong to deeply branching low-light-adapted clades that have no other cultivated representatives and display some unusual characteristics. For example, despite its otherwise low-light-adapted physiological characteristics, strain MIT1223 has low chl b2 content similar to high-light-adapted strains. Isolate genomes revealed that each strain contains a unique arsenal of pigment biosynthesis and binding alleles that have been horizontally acquired, contributing to the observed physiological diversity. Comparative genomic analysis of all picocyanobacteria reveals that Pcb, the major pigment carrying protein in Prochlorococcus, greatly increased in copy number and diversity per genome along a branch that coincides with the loss of facultative particle attachment. Collectively, these observations support a recently developed macroevolutionary model, in which niche-constructing radiations allowed ancestral lineages of picocyanobacteria to transition from a particle-attached to planktonic lifestyle and broadly colonize the euphotic zone.IMPORTANCEThe marine cyanobacterium, Prochlorococcus, is among the Earth's most abundant organisms, and much of its genetic and physiological diversity remains uncharacterized. Although field studies help reveal the scope of diversity, cultured isolates allow us to link genomic potential to physiological processes, illuminate eco-evolutionary feedbacks, and test theories arising from comparative genomics of wild cells. Here, we report the isolation and characterization of novel low-light (LL)-adapted Prochlorococcus strains that fill in multiple evolutionary gaps. These new strains are the first cultivated representatives of the LLVII and LLVIII paraphyletic grades of Prochlorococcus, which are broadly distributed in the lower regions of the ocean euphotic zone. Each of these grades is a unique, highly diverse section of the Prochlorococcus tree that separates distinct ecological groups: the LLVII grade branches between monophyletic clades that have facultatively particle-associated and constitutively planktonic lifestyles, whereas the LLVIII grade lies along the branch that leads to all high-light (HL)-adapted clades. Characterizing strains and genomes from these grades yields insights into the large-scale evolution of Prochlorococcus. The new LLVII and LLVIII strains are adapted to growth at very low irradiance levels and possess unique light-harvesting gene signatures and pigmentation. The LLVII strains represent the most basal Prochlorococcus group with a major expansion in photosynthetic antenna genes. Furthermore, a strain from the LLVIII grade challenges the paradigm that all LL-adapted Prochlorococcus exhibit high ratios of chl b:a2. These findings provide insights into the photophysiological evolution of Prochlorococcus and redefine what it means to be a low- vs high-light-adapted Prochlorococcus cell.

Microscopic Phage Adsorption Assay: High-throughput quantification of virus particle attachment to host bacterial cells.

Phages, viruses of bacteria, play a pivotal role in Earth's biosphere and hold great promise as therapeutic and diagnostic tools in combating infectious diseases. Attachment of phages to bacterial cells is a crucial initial step of the interaction. The classic assay to quantify the dynamics of phage attachment involves co-culturing and enumeration of bacteria and phages, which is laborious, lengthy, hence low-throughput, and only provides ensemble estimates of model-based adsorption rate constants. Here, we utilized fluorescence microscopy and particle tracking to obtain trajectories of individual virus particles interacting with cells. The trajectory durations quantified the heterogeneity in dwell time, the time that each phage spends interacting with a bacterium. The average dwell time strongly correlated with the classically-measured adsorption rate constant. We successfully applied this technique to quantify host-attachment dynamics of several phages including those targeting key bacterial pathogens. This approach should benefit the field of phage biology by providing highly quantitative, model-free readouts at single-virus resolution, helping to uncover single-virus phenomena missed by traditional measurements. Owing to significant reduction in manual effort, our method should enable rapid, high-throughput screening of a phage library against a target bacterial strain for applications such as therapy or diagnosis.

Flower-like NiFe layered double hydroxide/Bi2WO6 S-scheme heterojunction for photodegradation of ciprofloxacin under visible light

Photocatalytic degradation stands as an effective remedy to solve the global environmental pollution caused by organic pollutants. In this study, we synthesized a NiFe layered double hydroxide/Bi2WO6 (NF-LDH/BWO) Step-scheme (S-scheme) heterojunction. The attachment of NF-LDH particles on flower-like BWO increased the active sites and the interface area between two pure materials. The construction of LDH/BWO heterojunction endowed with improved light absorption capacity and boosted separation efficiency of photo-generated carriers. Consequently, compared with BWO and NF-LDH, the NF-LDH/BWO composites showed enhanced photoactivities. At NF-LDH mass ratio of 10%, the optimal degradation rate of ciprofloxacin (75.9%) within 60 min under visible illumination was achieved, 1.43- and 9.37-fold those of BWO and NF-LDH, respectively. In addition, the NF-LDH/BWO composite also demonstrated excellent cyclic stability. The S-scheme mechanism was proposed based on both experimental and density functional calculation results.

Coupled effects of iron (hydr)oxides and clay minerals on the heterogeneous oxidation of aqueous Mn(II) and crystallization of manganese (hydr)oxides

The formation of nanominerals and mineral nanoparticles (NMMNs) has drawn broad attention due to their high reactivity and omnipresence in the environment. While the heterogeneous formation of NMMNs on surfaces of various minerals has been extensively studied, there is limited understanding of how mineral heteroaggregates influence this process. In this study, we investigated how heteroaggregates of iron (hydr)oxides and clay minerals affect the heterogeneous oxidation of aqueous Mn(II) and crystallization of manganese (hydr)oxides (MnOx). Our results revealed that iron (hydr)oxides (ferrihydrite) and clay minerals (kaolinite or montmorillonite) in heteroaggregates exerted coupled effects on these processes, dictating the distribution of Mn and the morphology of MnOx. Specifically, ferrihydrite catalyzed gradual oxidative removal of Mn(II) and triggered MnOx nucleation; in contrast, kaolinite/montmorillonite rapidly adsorbed Mn(II) but hardly catalyzed its oxidation. These reactions collectively resulted in fast adsorption and gradual oxidation of Mn(II) on the heteroaggregates. Further, MnOx nanoparticles formed on ferrihydrite surfaces migrated to kaolinite/montmorillonite surfaces, leading to interactions between MnOx and various component minerals within the heteroaggregates. This significantly altered the subsequent growth pathways and the eventual morphology of MnOx. Consequently, while MnOx nanoparticles in the ferrihydrite-only system aggregated freely and formed well-extended nanowires, those in the ferrihydrite-kaolinite system predominantly became short nanorods due to the immobilization by kaolinite surfaces; in the ferrihydrite-montmorillonite system, considerable MnOx nanoparticles attached to montmorillonite surfaces due to strong electrostatic attraction, and subsequently grew into blocky particles via particle attachment. These findings illustrate that surface reactivities of heteroaggregated ferrihydrite and kaolinite/montmorillonite are coupled when they interact with aqueous Mn(II) or MnOx. Our work exemplifies, for the first time, the cooperation between surfaces of various minerals during the heterogeneous formation of NMMNs. Findings from this study also enhance our understanding of MnOx formation on surfaces with diverse atomic structures, and contribute to the knowledge of Mn cycling in the environment.

Ion Correlations Decrease Particle Aggregation Rate by Increasing Hydration Forces at Interfaces.

The connection between solution structure, particle forces, and emergent phenomena at solid-liquid interfaces remains ambiguous. In this case study on boehmite aggregation, we established a connection between interfacial solution structure, emerging hydration forces between two approaching particles, and the resulting structure and kinetics of particle aggregation. In contrast to expectations from continuum-based theories, we observed a nonmonotonic dependence of the aggregation rate on the concentration of sodium chloride, nitrate, or nitrite, decreasing by 15-fold in 4 molal compared to 1 molal solutions. These results are accompanied by an increase in repulsive hydration forces and interfacial oscillatory features from 0.27-0.31 nm in 0.01 molal to 0.38-0.52 nm in 2 molal. Moreover, molecular dynamics (MD) simulations indicated that these changes correspond to enhanced ion correlations near the interface and produced loosely bound aggregates that retain electrolyte between the particles. We anticipate that these results will enable the prediction of particle aggregation, attachment, and assembly, with broad relevance to interfacial phenomena.

Simultaneous 2D Projection and 3D Topographic Imaging of Gas-Dependent Dynamics of Catalytic Nanoparticles.

Catalyst deactivation through pathways such as sintering of nanoparticles and degradation of the support is a critical factor when designing high-performance catalysts. Here, structural changes of supported nanoparticle catalysts are investigated in controlled gas environments (O2, H2O, and H2) at different temperatures by imaging simultaneously the nanoparticle structures in 2D projection and the 3D surface-sensitive topography. Platinum nanoparticles on carbon support as a model system are imaged in an environmental transmission electron microscope (ETEM), with concurrent acquisition of high-angle annular dark field scanning TEM (HAADF-STEM) and secondary electron (SE) images. Particle migration and coalescence occurs and shows gas-dependent kinetics, with nanoparticles moving across and through the support during and after coalescence. The temperature required for motion is lower in O2 than in H2O and H2, explained through the nature of the gas/nanoparticle interactions. In O2 and H2, the carbon support degrades by trench formation along migration pathways, and the particles move continuously, indicating a chemical reaction between gas and support. In H2O gas, motion is more discontinuous and oriented particle attachment occurs, as expected from theoretical predictions. These results suggest that multimodal imaging in ETEM that combines HAADF-STEM and SE data provides comprehensive information regarding catalyst dynamics and degradation mechanisms.

Advanced Mathematical Model for the Transport of Aggregating Nanoparticles in Water Saturated Porous Media: Nonlinear Attachment and Particle Size‐Dependent Dispersion

AbstractA conceptual mathematical model was developed to describe the migration of aggregating nanoparticles in water saturated, homogeneous porous media with one‐dimensional uniform flow. Nanoparticles can be found suspended in the aqueous phase or attached reversibly and/or irreversibly onto the solid matrix. The Smoluchowski population balance equation (PBE) was used to model the process of particle aggregation and was coupled with the advection‐dispersion‐attachment equation to form a nonlinear transport model. Furthermore, an efficient and accurate solver for the PBE, and an iterative solver for the linear or nonlinear attachment equations were employed. The new numerical model was applied to nanoparticle transport experimental data available in the literature. Although, conventional transport models can be used to describe nanoparticle migration at low ionic strength conditions, such models might not be applicable for high ionic strength conditions, where aggregation becomes a dominant process. Aggregation is significantly affecting the transport characteristics of nanoparticles. Under high ionic strength conditions, the mass retention in the solid matrix of the porous medium increases, and a nonlinear particle attachment behavior may be observed. The proposed model performed remarkably well, successfully capturing numerous physical processes associated with nanoparticle transport, including particle‐size‐dependent dispersion. Ignoring the aggregation process and using conventional colloidal transport models to model nanoparticle transport may lead to erroneous results.

Corrigendum 2 to "Inferred pyrite growth via the particle attachment pathway in the presence of trace metals" by Domingos et al., 2023

Corrigendum 2 to "Inferred pyrite growth via the particle attachment pathway in the presence of trace metals" by Domingos et al., 2023

Mesoporous graphene-supported nanostructured nickel telluride for efficient electrocatalytic oxygen evolution reaction

The electrocatalytic oxygen evolution reaction (OER) imposes significant constraints on the operational overpotential of electrochemical energy devices, such as water electrolyzers, metal-air batteries, and fuel cells. However, the sluggish kinetics of OER reactions hinder these applications, which has prompted efforts to design more effective electrocatalysts. In this study, we have synthesized NiTe via in-situ growth into mesoporous graphene (MG), with varying nominal weight percentages (5- wt%, 10- wt%, and 15- wt%) of NiTe. The resulting NiTe/MG nanohybrids displayed hexagonally structured NiTe nanoparticles with a predominant (101) surface that promotes the OER kinetics. The wrinkled 3D mesoporous graphene scaffold facilitated the attachment and dispersion of NiTe particles of nanoscale on its surface, preventing their agglomeration. The porous characteristics of the MG significantly increased the high surface area of the NiTe/MG nanohybrids (583–671 m2 g−1), promoting enhanced accessibility of active sites and mass transport beneficial for the OER. Moreover, the altered electronic structure of the NiTe in the MG nanohybrid indicates enhancing O2 desorption during the OER. The optimized composition of the 10 wt% NiTe-loaded MG nanohybrid electrocatalyst demonstrates superior OER activity compared to other nanohybrids. It exhibits a small overpotential of 250 mV at 10 mA cm−2, a low Tafel slope of 63 mV dec−1 and maintained stability in 1 M KOH (pH = 14) as the electrolyte for a prolonged period. This enhanced OER activity is ascribed to the synergistic effect of MG’s high conductivity and the improved intrinsic activity of NiTe within the nanohybrid structure.

Efficient removal of nanoplastics from industrial wastewater through synergetic electrophoretic deposition and particle-stabilized foam formation

Microplastic particles have been discovered in virtually all ecosystems worldwide, yet they may only represent the surface of a much larger issue. Nanoplastics, with dimensions well below 1 µm, pose an even greater environmental concern. Due to their size, they can infiltrate and disrupt individual cells within organisms, potentially exacerbating ecological impacts. Moreover, their minute dimensions present several hurdles for removal, setting them apart from microplastics. Here, we describe a process to remove colloidally stable nanoplastics from wastewater, which synergistically combines electrophoretic deposition and the formation of particle-stabilized foam. This approach capitalizes on localized changes in particle hydrophilicity induced by pH fluctuations resulting from water electrolysis at the electrode surface. By leveraging these pH shifts to enhance particle attachment to nascent bubbles proximal to the electrode, separation of colloidal particles from aqueous dispersions is achieved. Using poly(methyl methacrylate) (PMMA) colloidal particles as a model, we gain insights into the separation mechanisms, which are subsequently applied to alternative model systems with varying surface properties and materials, as well as to real-world industrial wastewaters from dispersion paints and PMMA fabrication processes. Our investigations demonstrate removal efficiencies surpassing 90%.

Confined growth with particle attachment driven self-sieving for enhanced cascade reaction via versatile core-shell-shell nanocomposites

Controlling formation of metal organic frameworks (MOFs) with embedded enzymes on magnetic surface has been achieved by a confined growth with particle attachment driven self-sieving approach for the first time. Specifically, a versatile route of silica encapsulation guided enzyme assembly for formation of ZIF-8 shell has been successfully demonstrated by shaped-controllable Fe3O4 nanoparticles, e.g., nanorod and nanocube. Interestingly, silica encapsulation can lead to structural diversity of ZIF-8 shell on the shaped-controllable Fe3O4 nanoparticles for affecting properties of the nanocomposites. Furthermore, embedded enzymes confined between silica endoskeleton and ZIF-8 exoskeleton can participate in cascade reaction with different activities and stabilities in the terms of plasmonic assemblies fabrication and cancer cell catalytic therapy. As a result, a circulation plasmonic fabrication and cancer therapy can be achieved via the magnetic nanocomposites. It can be expected that the confined growth with particle attachment driven self-sieving method can be versatile to generate diverse MOFs shell encapsulated shaped-controllable nanoparticles for efficiently embedding enzyme in the nanocomposites.

Effect of Solvent Composition on Non-DLVO Forces and Oriented Attachment of Zinc Oxide Nanoparticles.

Oriented attachment (OA) occurs when nanoparticles in solution align their crystallographic axes prior to colliding and subsequently fuse into single crystals. Traditional colloidal theories such as DLVO provide a framework for evaluating OA but fail to capture key particle interactions due to the atomistic details of both the crystal structure and the interfacial solution structure. Using zinc oxide as a model system, we investigated the effect of the solvent on short-ranged and long-ranged particle interactions and the resulting OA mechanism. In situ TEM imaging showed that ZnO nanocrystals in toluene undergo long-range attraction comparable to 1kT at separations of 10 nm and 3kT near particle contact. These observations were rationalized by considering non-DLVO interactions, namely, dipole-dipole forces and torques between the polar ZnO nanocrystals. Langevin dynamics simulations showed stronger interactions in toluene compared to methanol solvents, consistent with the experimental results. Concurrently, we performed atomic force microscopy measurements using ZnO-coated probes for the short-ranged interaction. Our data are relevant to another type of non-DLVO interaction, namely, the repulsive solvation force. Specifically, the solvation force was stronger in water compared to ethanol and methanol, due to the stronger hydrogen bonding and denser packing of water molecules at the interface. Our results highlight the importance of non-DLVO forces in a general framework for understanding and predicting particle aggregation and attachment.

Influence of Pre- and Post-Contouring Strategies to Downskin Sloped Surfaces in Laser Powder-Bed Fusion (L-PBF) Additive Manufacturing.

Among various metal additive manufacturing (AM) technologies, L-PBF is known for fabricating intricate components. However, due to step edges and powder particle attachments, attaining a good surface finish is challenging, especially on downskin surfaces. Contour scanning has potential to improve surface quality because such scanning may dominate the surface formation of sloped features. This study evaluates the effects of pre- and post-contouring strategies on the sloped downskin surfaces fabricated using a commercial L-PBF system with Ti6Al4V powder. L-PBF parts printed at inclination angles 30°, 45° and 60° were investigated. A double-contouring approach with varying processing conditions was employed and surface characteristics were analyzed using data acquired by white light interferometry. The average surface roughness, Sa, surface skewness, Ssk, and percentage area of powder particles attached onto surfaces were statistically evaluated. The lowest Sa obtained for pre- and post-contoured samples is 14.08 µm and 18.88 µm, respectively. For both strategies, the combination of a low laser power and a high scan speed on the interface of downskin surface and underneath powder results in smoother surfaces. However, while comparing both strategies, pre-contouring gives better surface finish for samples built at similar processing conditions, with a difference of nearly 5 µm in Sa.

PSMA-Targeted Therapy: Advancements in Detection and Treatment Modalities with Dr. Scott T. Tagawa.

Prostate cancer is one of the most challenging malignancies due to its high incidence and prevalence, as it is the most frequently diagnosed non-skin cancer in men. The timely identification of prostate cancer and its metastasis is paramount for ensuring favorable outcomes for patients. Prostate-specific membrane antigen (PSMA) emerges as a promising biomarker for its detection, due to its specificity. This makes it an ideal target for the early identification of a metastatic phenotype. Situated on the membrane of tumor cells, PSMA facilitates the attachment of PSMA-targeting particles, enabling their detection through positron emission tomography (PET) scans with relative ease. Utilizing these imaging agents in conjunction with PET scans enhances the accuracy of prostate cancer tumor detection compared to PET scans alone. The advancement in prostate cancer imaging has paved the way for innovative treatment modalities. Prostate-specific membrane antigen-targeted radionuclide therapies (PSMA-TRT) exploit PSMA imaging agents to target identified prostate cancer malignancies with precise radiation, thereby reducing or eliminating the tumor mass. PSMA-TRT exhibits significant promise in prostate cancer therapy, evident from the notable declines in prostate-specific antigen (PSA) levels post treatment. However, PSMA-TRT carries both beneficial and adverse effects. While it represents a substantial leap forward in tumor cell imaging, PSMA-based antigens, being larger particles than ligands, offer prolonged imaging capabilities. Yet, the long-term effects of PSMA-TRT remain unknown, with the short-term adverse ones including fatigue, nausea, pain flares, and potential radiation exposure to others.

In Vitro Effect of 9,9'-Norharmane Dimer against Herpes Simplex Viruses.

Herpes simplex virus (HSV) infections are highly widespread among humans, producing symptoms ranging from ulcerative lesions to severe diseases such as blindness and life-threatening encephalitis. At present, there are no vaccines available, and some existing antiviral treatments can be ineffective or lead to adverse effects. As a result, there is a need for new anti-HSV drugs. In this report, the in vitro anti-HSV effect of 9,9'-norharmane dimer (nHo-dimer), which belongs to the β-carboline (βC) alkaloid family, was evaluated. The dimer exhibited no virucidal properties and did not impede either the attachment or penetration steps of viral particles. The antiviral effect was only exerted under the constant presence of the dimer in the incubation media, and the mechanism of action was found to involve later events of virus infection. Analysis of fluorescence lifetime imaging data showed that the nHo-dimer internalized well into the cells when present in the extracellular incubation medium, with a preferential accumulation into perinuclear organelles including mitochondria. After washing the host cells with fresh medium free of nHo-dimer, the signal decreased, suggesting the partial release of the compound from the cells. This agrees with the observation that the antiviral effect is solely manifested when the alkaloid is consistently present in the incubation media.

Black titania coated glass fiber as a photo absorber in interfacial solar steam generation under harsh condition

Interfacial solar steam generation (ISSG) is one of the promising solutions in the field of water filtration, desalination, and solvent recovery. For the industrial applications of the technology, there is a need for developing highly durable, thermally stable, and inert light absorbers. Therefore, this work addresses this issue by synthesizing black Titania (B–TiO2) via vacuum annealing and depositing it on glass fiber (GF) via vacuum filtration with an ethyl cellulose binder. According to the characterization techniques analyses, the change of colour is attributed to the occurrence of oxygen vacancies in the surface layers of TiO2 nanoparticles during vacuum annealing. The deposition parameters were optimized for achieving a maximum solar-weighted light absorptance of 95.7%. The optimized B–TiO2 GF was applied for the steam generation experiments and achieved the evaporation rate of 1.53 kg m−2 h−1, which corresponds to solar-steam conversion efficiency of 97.7 % under standard measurements condition of AM 1.5 G sun and ambient temperature and relative humidity of 20 °C and 40% respectively. Thanks to the high durability and chemical inertness of B–TiO2 GF it was applied for water filtration in extreme conditions of acidic/alkaline water and high-sun illumination (up to 35-sun). Worth noting that for high-sun experimentation there is a need to use a binder to improve particle attachment to the glass fibers.

Competition for resources in an exclusion model with biased lane-changing mechanism.

The motivation for the proposed work is drawn from the attachment-detachment observed in biological and physical transport processes that entail finite resources. We investigate the influence of limited particle availability on particle dynamics within two parallel totally asymmetric simple exclusion lanes, with one lane incorporating only particle detachment and the other considering particle attachment. We establish a theoretical framework by employing vertical mean-field theory in conjunction with singular perturbation technique. The analytical findings are supported by numerical and stochastic validation using a finite-difference scheme and the Gillespie algorithm. By utilizing these approaches, we scrutinize various stationary properties, including particle densities, phase boundaries, and particle currents for both lanes. Our analysis reveals that the complexity of the phase diagram exhibits a nonmonotonic trend in the number of stationary phases as the particle count increases. Each phase diagram is constructed with respect to the intrinsic boundary parameters, illustrating both bulk and surface transitions occurring within the lanes. The interplay between finite resources and coupling mechanisms gives rise to two phases involving upward shock in one of the lanes, while two phases exhibit synchronized downward shock in both lanes. Finally, we delve into shock dynamics to comprehend critical phase transitions occurring in the system.

Tailoring the surface features of CaWO4 by coupling with tubular g-C3N4 for enhanced solar photocatalysis and thermal energy storage

Rising energy and environmental crisis has led researchers to develop novel bifunctional materials. Herein, we report the construction of bifunctional hybrid materials for thermal energy storage and solar photocatalytic systems. Such a novel type of green material including calcium tungstate (CaWO4) and tubular graphitic carbon nitride (g-C3N4) was successfully fabricated via thermal mixing method. X-ray diffraction analysis confirmed the formation of both CaWO4 and g-C3N4 in the composite while morphological analyses verified the successful attachment of CaWO4 particles over the tubular g-C3N4 structure. The wide band gap energy (3.6 eV) of the pristine CaWO4 significantly decreased to 1.85 eV after coupling with g-C3N4. The hybrid catalyst showed superior photocatalytic degradation of Allura red (79.3 % within 120 min) and the rate constant was found 31.3-folds higher compared to pristine CaWO4 (13.3 % removal), which was ascribed to strong light harvesting, increased surface area, smaller crystallite size and fast electron transfer rate. In addition to catalytic functionality, the synthesized pristine and hybrid catalysts were also used in the preparation of lauric acid-based phase change materials (PCMs) and thermal properties of different fillers were examined. The 1 wt% CaWO4/g-C3N4 filler loaded composite displayed 13.03 % increment in heat storage rate (oC/s) when compared with lauric acid, demonstrating the essential role of the hybrid material over the PCM structure. The as-prepared hybrid materials displayed a bifunctional activity derived from incorporation of carbon nitride and thus verified a great potential for different applications due to their enhanced features.

MOR nanosheets with tunable c-axis thickness and their catalytic performance in DME carbonylation

Controlling the anisotropic growth of crystals to achieve desired morphology is a challenge in zeolite crystallization, which often requires the use of bulky organic surfactants or additional crystal growth modifiers. Here, MOR crystals with tunable c-axis thickness (12-MR channel direction) were readily synthesized with commercial tetraethylammonium hydroxide (TEAOH) as an organic-structure directing agent (OSDA). It is revealed that the relative growth rates of different crystal faces of MOR zeolite can be tuned by the crystallization temperature and TEAOH amount in the developed gel system. Higher temperature and lower TEAOH concentration can effectively retard the growth of MOR crystals along the c-axis, yielding MOR nanosheets with short c-axis thickness (ca. 40 nm). Investigation on the crystallization process demonstrates that the crystal growth follows a particle attachment mechanism. Theoretical calculation was further employed to elucidate the c-axis thickness variation of MOR zeolite under different conditions. A kilogram-scale synthesis of MOR nanosheets has been realized with a 10 L autoclave, achieving high solid yield of 92 %. The MOR nanosheets, offering short 12-MR diffusion path, exhibit substantially enhanced catalytic activity and stability in the dimethyl ether (DME) carbonylation to methyl acetate reaction.