Bulk Characterization Research Articles

On the Origin of the Non-Arrhenius Na-ion Conductivity in Na3OBr.

The sodium-rich antiperovskites (NaRAPs) with composition Na3OB (B=Br, Cl, I, BH4, etc.) are a family of materials that has recently attracted great interest for application as solid electrolytes in sodium metal batteries. Non-Arrhenius ionic conductivities have been reported for these materials, the origin of which is poorly understood. In this work, we combined temperature-resolved bulk and local characterisation methods to gain an insight into the origin of this unusual behaviour using Na3OBr as a model system. We first excluded crystallographic disorder on the anion sites as the cause of the change in activation energy; then identified the presence of a poorly crystalline impurities, not detectable by XRD, and elucidated their effect on ionic conductivity. These findings improve understanding of the processing-structure-properties relationships pertaining to NaRAPs and highlight the need to determine these relationships in other materials systems, which will accelerate the development of high-performance solid electrolytes.

Real-time imaging of acoustic waves in bulk materials with X-ray microscopy

The dynamics of lattice vibrations govern many material processes, such as acoustic wave propagation, displacive phase transitions, and ballistic thermal transport. The maximum velocity of these processes and their effects is determined by the speed of sound, which therefore defines the temporal resolution (picoseconds) needed to resolve these phenomena on their characteristic length scales (nanometers). Here, we present an X-ray microscope capable of imaging acoustic waves with subpicosecond resolution within mm-sized crystals. We directly visualize the generation, propagation, branching, and energy dissipation of longitudinal and transverse acoustic waves in diamond, demonstrating how mechanical energy thermalizes from picosecond to microsecond timescales. Bulk characterization techniques capable of resolving this level of structural detail have previously been available on millisecond time scales-orders of magnitude too slow to capture these fundamental phenomena in solid-state physics and geoscience. As such, the reported results provide broad insights into the interaction of acoustic waves with the structure of materials, and the availability of ultrafast time-resolved dark-field X-ray microscopy opens a vista of new opportunities for 3D imaging of materials dynamics on their intrinsic submicrosecond time scales.

Probing individual single atom electrocatalyst sites by advanced analytical scanning transmission electron microscopy

Single atom electrocatalysts (SAEs) are promising next-generation materials for promoting a variety of important reactions, such as the oxygen reduction, nitrogen reduction, and CO2 reduction reactions. While bulk characterization techniques such as X-ray absorption spectroscopy and Mössbauer spectroscopy have significantly enhanced our understanding of these catalysts, direct probing of individual single metal atom sites at the atomic scale is necessary to understand local variations in the properties of these sites and accelerate design and synthesis of improved SAEs. Aberration-corrected scanning transmission electron microscopy (STEM) has become a powerful tool for providing this type of atomic-scale information about SAE metal sites. These sites are typically unstable under the electron beam, however, which, in combination with conventional acquisition methods and detectors, has limited the type and quantity of information obtainable by spectroscopic STEM techniques. Here, we map multiple individual SAE metal sites in a nitrogen-doped carbon containing atomically dispersed Fe and Re (FeReNC) at the atomic scale by direct electron detection electron energy-loss spectroscopy (EELS). Direct electron detection provides an improved signal-to-noise ratio over conventional scintillator-based detectors and enables detection and real space localization of weak signals. In addition, we demonstrate an automated method for identification of metal atom positions, placement of the probe on these sites, and simultaneous EELS and energy dispersive X-ray spectroscopic (EDS) signal acquisition. This simultaneous acquisition of EELS and EDS provides access to the composition and bonding of a wide range of SAE metal sites. Focusing the probe directly on the metal sites also increases the relevant data acquisition rate by more than an order of magnitude over two-dimensional mapping, enabling improved statistical measurements of site properties. The versatility, sensitivity, and speed that these techniques provide enhances our ability to probe the local elemental and chemical environment of a large number of individual SAE metal site structures at the atomic scale, enabling an improved understanding of the variations in the local properties of these electrocatalysts to be gained. As a result, significantly increased information about individual metal sites will be available to future electrochemical studies through these techniques, accelerating the development of advanced SAEs.

Polarization Resolved Fluorescence Detection of Carbon Nanotube Corona Phases

Circular dichroism measures how chiral particles absorb right- and left- circularly polarized light differently to distinguish pairs of enantiomers. It can also elucidate differential photoabsorption of chiral fluorescent species via their emissions. However, this method has generally been restricted to bulk samples. Hence, these methods conceal information on the specific chiroptical response of a single particle. Furthermore, circular dichroism has been restricted in time- resolution as well as spectral range. In this work, we observed fluorescence detected circular dichroism (FDCD) of individually deposited single walled carbon nanotube (SWNT) corona. A custom-built setup compromising a linear polarizer (LP) and a quarter waveplate (QWP) was used to induce circularly polarized light (CPL). The light polarization state at the sample plane was analyzed using Stoke’s parameter. Experimental results showed that linear dichroism of the dichroic filter inside the microscope changes the polarization state of the incoming beam drastically, and thus inducing elliptically polarized light at the sample plane. A liquid crystal variable retarded (LCVR) was used to correct the polarization state of light and yield CPL at the sample plane. Singly-dispersed SWNT with different wrapping polymers were deposited onto a glass substrate. Alternating cycles of right- and left-handed circularly polarized light was delivered to excite the sample. The fluorescence intensities of each individual SWNT were tracked. The dissymmetry (g) parameters: g = 2(IL-IR)/(IL+IR) (where I L and I R are the measured fluorescence intensities with left and right circularly polarized light, respectively) were analyzed from the fluorescent signals to understand photoabsorption differences. A non-zero value of dissymmetry parameter provides information on how the corona modulates SWNT photoluminescence, an outcome not observable by bulk characterization methods. This observation can potentially enable the measurement of chiral species local interactions without a separations process.

Design of refractory multi-principal-element alloys for high-temperature applications

Refractory multi-principal-element alloys (RMPEAs) exhibit high specific strength at elevated temperatures (T). However, current RMPEAs lack a balance of room-temperature (RT) ductility, high-T strength, and high-T creep resistance. Using density-functional theory methods, we scanned composition space using four criteria: (1) formation energies for operational stability: -150le {E}_{{rm {f}}} ≤ +70 meV per atom; (2) higher strength found via interstitial electron density with Young’s moduli E > 250 GPa; (3) inverse Pugh ratio for ductility: G/B < 0.57; and (4) high melting points: Tm > 2500 °C. Using rapid bulk alloy synthesis and characterization, we validated theory and down-selected promising alloy compositions and discovered Mo72.3W12.8Ta10.0Ti2.5Zr2.5 having well-balanced RT and high-T mechanical properties. This alloy has comparable high-T compressive strength to well-known MoNbTaW but is more ductile and more creep resistant. It is also superior to a commercial Mo-based refractory alloy and a nickel-based superalloy (Haynes-282) with improved high-T tensile strength and creep resistance.

Bulk characterization of highly structured tissue paper based on 2D and 3D evaluation methods

The structure of the fibre network in tissue paper can be complex and difficult to analyze, due to the presence of superimposed structures such as creping and patterns that occur, for example, in through-air-dried (TAD) tissue. Properties like high absorbency, a pleasant handfeel, and strength-related characteristics are closely related to the fibre network structure. Therefore, in addition to standard tissue testing methods, techniques that provide insights into the intrinsic properties of the tissue fibre network are essential for a deeper understanding and potential for further optimization. In this study, we utilized 2D cross-sectional images and 3D X-ray microtomography (mu-CT) to evaluate and quantify the intrinsic properties of highly structured TAD tissue. We compared the results obtained from these two methods, focusing on intrinsic thickness, porosity, and the fibre volume to fibre surface area (Fv/Fs) ratio. The open structure of the fibre network, fabric patterns, creping, and protruding fibres make it challenging to define bulk boundaries. Therefore, we examined the effect of different bulk expansion diameters on intrinsic properties. This procedure allows to quantify the effects of under- and overestimation of bulk boundaries, and to determine which regions within the fibre network are affected by bulk expansion. In terms of intrinsic thickness, both 2D and 3D evaluations show similar trends, which facilitates direct comparison of 2D and 3D data. Porosity, on the other hand, does not show any correlation between 2D and 3D-based data. Together with the Fv/Fs parameter, this leads to the conclusion that the depiction of 2D data does not represent the whole fibrous material but predominantly fibres perpendicular or close to perpendicular to the cut plane, whereas 3D data represents all fibres, fibre bonds and network connectivity. This work aims at presenting modern approaches and novel procedures to quantify intrinsic properties of open fibre structures such as tissue, but could also be applied to fibrous networks in general. The introduced methods could provide the basis for future research on the interrelations between intrinsic properties and key tissue properties such as absorbency and handfeel.

Melt pool boundaries in additively manufactured AlSi10Mg: Correlating inhomogeneous deformation with local microstructure via in-situ microtensile tests

Microstructures in additively manufactured metals are often inhomogeneous and complex. Melt pool (MP) centers and boundaries can vary significantly, such as in AlSi10Mg, where MP boundaries reveal a coarsening and breakdown of the refined cellular network. However, bulk characterization techniques often lack the resolution to quantify the local deformation on the length scale of a melt pool boundary which ranges from 1 to 100 μm. Here, in-situ scanning electron microscopy (SEM) microtensile experiments on AlSi10Mg samples were used to compare the relative yield behavior and deformation uniformity throughout microstructural regions, particularly around the MP boundaries. Differences in the local mechanical response – deformation, strain hardening, and yield – are reported between the MP boundaries and centers. These differences in deformation are correlated to specific microstructural features like cell size, cell connectedness, cell eccentricity, and grain size. Quantitative correlations of local deformation with relevant microstructural features, as presented here, will aid modelers and the additive manufacturing (AM) community to more precisely predict and control AM AlSi10Mg part performance.

Multi‐Phase Sputtered TiO2‐Induced Current–Voltage Distortion in Sb2Se3 Solar Cells

AbstractDespite the recent success of CdS/Sb2Se3 heterojunction devices, cadmium toxicity, parasitic absorption from the relatively narrow CdS band gap (2.4 eV) and multiple reports of inter‐diffusion at the interface forming Cd(S,Se) and Sb2(S,Se)3 phases, present significant limitations to this device architecture. Among the options for alternative partner layers in antimony chalcogenide solar cells, the wide band gap, non‐toxic titanium dioxide (TiO2) has demonstrated the most promise. It is generally accepted that the anatase phase of the polymorphic TiO2 is preferred, although there is currently an absence of analysis with regard to phase influence on device performance. This work reports approaches to distinguish between TiO2 phases using both surface and bulk characterization methods. A device fabricated with a radio frequency (RF) magnetron sputtered rutile‐TiO2 window layer (FTO/TiO2/Sb2Se3/P3HT/Au) achieved an efficiency of 6.88% and near‐record short–circuit current density (Jsc) of 32.44 mA cm−2, which is comparable to established solution based TiO2 fabrication methods that produced a highly anatase‐TiO2 partner layer and a 6.91% efficiency device. The sputtered method introduces reproducibility challenges via the enhancement of interfacial charge barriers in multi‐phase TiO2 films with a rutile surface and anatase bulk. This is shown to introduce severe S‐shaped current–voltage (J–V) distortion and a drastic fill–factor (FF) reduction in these devices.

Integrated single-cell and bulk characterization of cuproptosis key regulator PDHB and association with tumor microenvironment infiltration in clear cell renal cell carcinoma.

Renal clear cell carcinoma (ccRCC) is one of the most prevalent cancers worldwide. Accumulating evidence revealed that copper-induced cell death played a vital role in various tumors. However, the underlying mechanism of cuproptosis with molecular heterogeneity and tumor microenvironment (TME) in ccRCC remains to be elucidated. The present study aimed to discover the biological function of cuproptosis regulators with the potential to guide clinical therapy. Using Single-cell RNA-seq, bulk transcriptome and other multi-omics datasets, we identify essential cuproptosis-related hub gene PDHB for further study. The dysregulation of PDHB in ccRCC was characterized, together with survival outcomes, pathway enrichment and immune infiltration among tumor microenvironments. The functional significance and clinical association of PDHB was validated with loss of function experiments and surgical removal specimens. PDHB mRNA and protein expression level was significantly downregulated in ccRCC tissues compared with normal and paired normal tissues. Clinicopathological parameters and tissue microarray (TMA) indicated that PDHB was identified as a prognostic factor for survival outcomes among ccRCC patients. Additionally, low PDHB was negatively correlated with Treg cells, indicating an immunosuppressive microenvironment. Mechanistically, knockdown PDHB appeared to promote the RCC cells proliferation, migration, and invasion potentials. Subsequent studies showed that copper-induced cell death activation could overcome sunitinib resistance in RCC cells. This research illustrated a cuproptosis-related hub gene PDHB which could serve as a potential prognostic marker and provide therapeutic benefits for clinical treatment of ccRCC patients.

Photo-epoxidation of α-pinene catalyzed by a MoVI oxo-diperoxo complex modified Ti-based metal-organic framework

An oxo-diperoxo molybdenum (VI) complex was anchored on a MIL-125-NH2 Metal-Organic Framework (MOF), and its Oxygen Atom Transfer (OAT) catalytic performance in the photo-epoxidation of α-pinene was evaluated. MIL-125-NH2 was modified with salicylaldehyde and pyridine-2-aldehyde by a post-synthetic approach to produce Schiff base ligands. Then, a MoVI complex was incorporated into the resulting MOFs. Bulk and surface characterization evidenced the incorporation of the Shiff base ligands and the MoO(O2)2 complex inside the Ti-MOF by studying the effect on the properties of each post-synthetic step. The final MOFs effectively achieved the transfer of 4 oxygen atoms to 4 olefin molecules during the irradiation but without the presence of any oxidant. The complete reoxidation of the oxo-Mo-center with O2 was reached since it presented the same catalytic activity after the oxygenation cycle. Also, α-pinene oxide resulted as the main product of photoinduced OAT long-term reaction, showing high performance in the epoxidation of olefins.

Bulk Flow Optimisation of Amorphous Solid Dispersion Excipient Powders through Surface Modification.

Particulate amorphous solid dispersions (ASDs) have been recognised for their potential to enhance the performance of various solid dose forms, especially oral bioavailability and macromolecule stability. However, the inherent nature of spray-dried ASDs leads to their surface cohesion/adhesion, including hygroscopicity, which hinders their bulk flow and affects their utility and viability in terms of powder production, processing, and function. This study explores the effectiveness of L-leucine (L-leu) coprocessing in modifying the particle surface of ASD-forming materials. Various contrasting prototype coprocessed ASD excipients from both the food and pharmaceutical industries were examined for their effective coformulation with L-leu. The model/prototype materials included maltodextrin, polyvinylpyrrolidone (PVP K10 and K90), trehalose, gum arabic, and hydroxypropyl methylcellulose (HPMC E5LV and K100M). The spray-drying conditions were set such that the particle size difference was minimised, so that it did not play a substantial role in influencing powder cohesion. Scanning electron microscopy was used to evaluate the morphology of each formulation. A combination of previously reported morphological progression typical of L-leu surface modification and previously unreported physical characteristics was observed. The bulk characteristics of these powders were assessed using a powder rheometer to evaluate their flowability under confined and unconfined stresses, flow rate sensitivities, and compactability. The data showed a general improvement in maltodextrin, PVP K10, trehalose and gum arabic flowability measures as L-leu concentrations increased. In contrast, PVP K90 and HPMC formulations experienced unique challenges that provided insight into the mechanistic behaviour of L-leu. Therefore, this study recommends further investigations into the interplay between L-leu and the physico-chemical properties of coformulated excipients in future amorphous powder design. This also revealed the need to enhance bulk characterisation tools to unpack the multifactorial impact of L-leu surface modification.

Sonication-assisted liquid exfoliation and size-dependent properties of magnetic two-dimensional α-RuCl3

Originating from the hexagonal arrangement of magnetic ions in the presence of strong spin orbit coupling, α-RuCl3 is considered as model system for the Kitaev-Heisenberg model. While the magnetic properties of α-RuCl3 have been studied in bulk single crystals or micromechanically-exfoliated nanosheets, little is known about the nanosheets’ properties after exfoliation by techniques suitable for mass production such as liquid phase exfoliation (LPE). Here, we demonstrate sonication-assisted LPE on α-RuCl3 single crystals in an inert atmosphere. Coupled with centrifugation-based size selection techniques, the accessible size- and thickness range is quantified by statistical atomic force microscopy. Individual nanosheets obtained after centrifugation-based size selection are subjected to transmission electron microscopy to confirm their structural integrity after the exfoliation. The results are combined with bulk characterisation methods, including Raman and x-ray photoelectron spectroscopy, and powder diffraction experiments to evaluate the structural integrity of the nanosheets. We report changes of the magnetic properties of the nanomaterial with nanosheet size, as well as photospectroscopic metrics for the material concentration and average layer number. Finally, a quantitative analysis on environmental effects on the nanomaterial integrity is performed based on time and temperature dependent absorbance spectroscopy revealing a relatively slow decay (half-life of ∼2000 h at 20 °C), albeit with low activation energies of 6–20 kJ mol−1.

Abstract 1516: Bulk and spatial single-cell transcriptomic characterization of fibrolamellar hepatocellular carcinoma

Abstract Fibrolamellar Hepatocellular Carcinoma (FLC) is a rare liver cancer affecting adolescents and young adults, with no gender or ethnicity predilection and without history of underlying viral hepatitis, cirrhosis, or other known risk factors. Almost all FLC patients present a somatic heterozygous deletion in chromosome 19p13.12, DNAJB1::PRKACA, which is sufficient to drive FLC in mice. A few studies comparing FLC tumors with adjacent non-transformed liver (normal) samples revealed many transcriptional differences. However, there were done in very small datasets and analyzed using different bioinformatic methods, resulting in just 18-47% agreement between them. This study aims to comprehensively characterize the transcriptome of FLC at bulk and spatial single-cell resolution. The whole transcriptome of 109 FLC frozen patient samples, the largest RNA-seq dataset of FLC to date, was sequenced using different library preparation and ribosomal depletion methods. Only paired tumor and normal tissue samples resected from the same patient were used and divided into two groups: exploration (3 datasets, 67 samples) and testing (2 datasets, 17 samples). Additionally, as external validation datasets, RNA-seq samples from previously published studies were collected, including Sorenson et al. (FLC: 26, normal: 9, paired: 8), the TCGA-LIHC study (FLC: 6, normal: 1, paired: 1), Hirsch et al. (FLC: 15, normal: 3, paired: 0) and Francisco et al. (FLC: 27, normal: 10, paired: 9). All were reanalyzed using state-of-the-art bioinformatic methods: mapped to the Human Genome GRCh38.103 and transcripts quantified using Salmon 1.6.0, unsupervised clustering exploration using PCA, tSNE and UMAP, differential expression calculated using DESeq2 1.28.1, and checking for detectability and consistency among datasets. We found 857 up- and 988 down-regulated genes presenting the same dysregulation in the exploration datasets and confirmed in the testing and external datasets. We call these genes the transcriptional FLC signature. The FLC signature was further characterized by comparing it with the genes differentially expressed in other liver cancers: hepatocellular carcinoma (41 paired samples), hepatoblastoma (22 paired samples), and cholangiocarcinoma (27 paired samples). We found 276 up- and 352 down-regulated genes altered in other liver cancers as well as FLC, but 156 up- and 68 down-regulated only in FLC. The 112 genes with the strongest dysregulation (56 up and 56 down) were used for a MERFISH screening, providing for the first time a single-cell spatial transcriptomic characterization of FLC. This showed clear differential expression patterns in tumor, normal, stromal, and infiltrating immune cells, allowing the identification of how different cell types contribute to the transcriptional FLC signature. Citation Format: David Requena, Aldhair Medico, Luis F. Soto, Mahsa Shirani, James A. Saltsman, Gadi Lalazar, Michael P. LaQuaglia, Sanford M. Simon. Bulk and spatial single-cell transcriptomic characterization of fibrolamellar hepatocellular carcinoma [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2023; Part 1 (Regular and Invited Abstracts); 2023 Apr 14-19; Orlando, FL. Philadelphia (PA): AACR; Cancer Res 2023;83(7_Suppl):Abstract nr 1516.

Fabrication and characterization of hybrid bulk and surface acoustic wave resonators with Ag/patterned-AlN/Mo/diamond/Si layered structure

Hybrid bulk acoustic wave and surface acoustic wave (BAW/SAW) devices attract extensive interests due to their high electromechanical coupling coefficient and quality factor. In this study, longitudinal BAW coupled SAW resonators with piezoelectric AlN inter-digital transducers (IDT) were simulated and fabricated on diamond substrates to increase the working frequency as well. The simulated figure of merit value is 104, 123 % improved comparing with the corresponding metal IDT of 46.5. The frequency response spectrum of single port reflection (S11) shows dominant harmonic resonance at 913 MHz with electromechanical coupling coefficient of 2.16 % and quality factor of 913. These results indicate mutual transductions between BAW and SAW occur with sufficient efficiency in hybrid structures, which is analyzed and interpreted by equivalent acoustic impedance theory.

Choosing Carbon Conductive Additives for NMC-LATP Composite Cathodes: Impact on Thermal Stability

One of the main technological challenges oxide-based solid-state batteries face today is the densification of their components to reach good interfacial contact. The most common approach requires co-sintering of the different components (electroactive material, catholyte and conducting additive) at high temperatures which often results in the inter-diffusion of elements that deteriorate the overall cathode performance. In this work, the impact of different carbon grades in the thermal response of LATP-NMC622-Carbon electrodes is evaluated and shown to significantly influence the chemical compatibility between components. By means of a combination of bulk and surface characterization techniques including gas adsorption, X-ray diffraction, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and thermogravimetric analysis, it is shown that carbons with low surface area are more adequate as result in higher oxidation temperatures and hence are less reactive.

Time-of-flight neutron diffraction applied to the identification of crystalline phases in historical mosaic glasses

We present a completely non-destructive study of the crystalline phases present in the vitreous matrix of ancient mosaic glass tesserae, based on the application of the time-of-flight neutron diffraction (ToF-ND) technique. In contrast, standard phase analysis techniques may involve a sample preparation step, which is not compatible with the requirement of damage prevention of archaeological artefacts. Moreover, superficial or spot investigation by standard methods may not provide a complete description of the samples, especially in the case of inhomogeneous materials such as mosaic glasses, whereas ToF-ND can investigate the whole glass composition at the centimetre scale. The present study aims to obtain a bulk characterization of the glasses in terms of their mineralogical phase composition. Six glass specimens of ancient mosaic glass tesserae, that had been previously analysed with other non-destructive techniques to obtain their chemical and phase composition, were investigated by ToF-ND. These tesserae come from archaeological excavations or mosaics under restoration from different archaeological sites and geographical areas (Italy, Greece, and Syria) and date from the 1st to the 11th century AD. Several crystalline phases based on Ca, Sb, Sn, Cu and Pb minerals were identified, confirming the mineralogical phases identified with Raman spectroscopy in previous analyses. In addition, several other phases were identified for five of the samples. It is concluded that ToF-ND is an extremely important complementary tool for non-destructive bulk investigations of mosaic glass tesserae, which can overcome the heterogeneity of this kind of archaeological material.

Bulk and single-cell characterisation of the immune heterogeneity of atherosclerosis identifies novel targets for immunotherapy

BackgroundImmune cells that infiltrate lesions are important for atherosclerosis progression and immunotherapies. This study was aimed at gaining important new insights into the heterogeneity of these cells by integrating the sequencing results of multiple samples and using an enhanced single-cell sequencing workflow to overcome the limitations of a single study.ResultsIntegrative analyses identified 28 distinct subpopulations based on gene expression profiles. Further analysis demonstrated that these cells manifested high heterogeneity at the levels of tissue preferences, genetic perturbations, functional variations, immune dynamics, transcriptional regulators, metabolic changes, and communication patterns. Of the T cells, interferon-induced CD8+ T cells were involved in the progression of atherosclerosis. In contrast, proinflammatory CD4+ CD28null T cells predicted a poor outcome in atherosclerosis. Notably, we identified two subpopulations of foamy macrophages that exhibit contrasting phenotypes. Among them, TREM2- SPP1+ foamy macrophages were preferentially distributed in the hypoxic core of plaques. These glycolytic metabolism-enriched cells, with impaired cholesterol metabolism and robust pro-angiogenic capacity, were phenotypically regulated by CSF1 secreted by co-localised mast cells. Moreover, combined with deconvolution of the bulk datasets, we revealed that these dysfunctional cells had a higher proportion of ruptured and haemorrhagic lesions and were significantly associated with poor atherosclerosis prognoses.ConclusionsWe systematically explored atherosclerotic immune heterogeneity and identified cell populations underlying atherosclerosis progression and poor prognosis, which may be valuable for developing new and precise immunotherapies.

Green Light Photoelectrocatalysis with Sulfur-Doped Carbon Nitride: Using Triazole-Purpald for Enhanced Benzylamine Oxidation and Oxygen Evolution Reactions.

Materials dictate carbon neutralindustrialchemicalprocesses. Visible-light photoelectrocatalysts from abundant resources will play a key role in exploiting solar irradiation. Anionic doping via pre-organization of precursors and further co-polymerization creates tuneable semiconductors. Triazole derivative-purpald, an unexplored precursor with sulfur (S) container, combined in different initial ratios with melamine during one solid-state polycondensation with two thermal steps yields hybrid S-doped carbon nitrides (C3 N4 ). The series of S-doped/C3 N4 -based materials show enhanced optical, electronic, structural, textural, and morphological properties and exhibit higher performance in organic benzylamine photooxidation, oxygen evolution, and similar energy storage (capacitor brief investigation). 50M-50P exhibits the highest photooxidation conversion (84±3%) of benzylamine to imine at 535nm - green light for 48h, due to a discrete shoulder (≈700)nm, high sulfur content, preservation of crystal size, new intraband energy states, structural defects by layer distortion, and 10-16nm pores with arbitrary depth. This work innovates by studying the concomitant relationships between: 1) the precursor decomposition while C3 N4 is formed, 2) the insertion of Simpurities, 3) the S-doped C3 N4 property-activity relationships, and 4) combinatorial surface, bulk, structural, optical, and electronic characterization analysis. This work contributes to the development of disordered long-visible-lightphotocatalysts for solar energy conversion and storage.

Synergetic Regulation of the Microstructure and Acidity of HZSM-5/MCM-41 for Efficient Catalytic Cracking of n-Decane.

Alkane catalytic cracking is regarded as one of the most significant processes for light olefin production; however, it suffers from serve catalyst deactivation due to coke formation. Herein, HZSM-5/MCM-41 composites with different Si/Al2 ratios were first prepared by the hydrothermal method. The physicochemical properties of the prepared catalysts were analyzed by a series of bulk and surface characterization methods, and the catalytic performance was tested in n-decane catalytic cracking. It was found that HZSM-5/MCM-41 showed a higher selectivity to light olefins and a lower deactivation rate compared with the parent HZSM-5 due to an enhanced diffusion rate and decreased acid density. Moreover, the structure-reactivity relationship revealed that conversion, light olefin selectivity, and the deactivation rate strongly depended on the total acid density. Furthermore, HZSM-5/MCM-41 was further extruded with γ-Al2O3 to obtain the catalyst pellet, which showed an even higher selectivity to light olefins (∼48%) resulting from the synergy effect of the fast diffusion rate and passivation of external acid density.

Tuning anatase to rutile ratio in nanocrystalline titania enriched from sustainable beach sand from Cox's Bazar, Bangladesh

A sustainable source of titania (TiO2) is important in applications of photovoltaic devices, photocatalysts, sensors, and so forth. Beach sand from Cox's Bazar, Bangladesh, can be an excellent sustainable source of this titania as almost a quarter of it contains titania in the form of rutile and ilmenite. This study demonstrates the success of a sulfuric acid‐based hydrometallurgical process in enriching titania in Cox's Bazar beach sand. The route produces precursors that can be conveniently calcined into nanocrystalline phase‐pure anatase or anatase/rutile composites. We used both bulk and surface characterization to determine phase purity, crystallite size as well as surface chemistry, and morphology of the resulting anatase and rutile/anatase mixture. The proportion of anatase/rutile can be tuned by varying digestion times. This hydrometallurgical route can potentially lead to the scalable production of precursors used in producing high‐performance nanocrystalline titania from a sustainable source of beach sand from Cox's Bazar of Bangladesh.