Crystal Modification Research Articles

Recent Progress of Thin Crystal Engineering for Perovskite Solar Cells.

Metal halide perovskite single crystals hold promise for photovoltaics with high efficiency and stability due to their superior optoelectronic properties and weak bulk ion migration. The past several years have witnessed rapid development of single-crystal perovskite solar cells (PSCs) with efficiency rocketed from 6.5% to 24.3%, however, which still lags behind their polycrystalline counterparts. Moreover, the poor device stability under light illumination is contrary to the high ion migration barrier of perovskite single crystals. The key limiting factors should be the low crystalline quality and high surface defect density of solution-grown thin single crystals. Under this circumstance, a review paper summarizing the recent progress and challenges will be instructive for future development of this emerging field. In this manuscript, the crystal engineering used to enhance carrier transport and suppress carrier recombination in vertical single-crystal PSCs will be summarized initially, including crystal growth, component control, surface and interface modification. Subsequently, the application of perovskite single crystals in lateral single-crystal PSCs will be discussed and compared with the conventionally vertical structure. Finally, the challenges and proposed strategies for the development of single-crystal PSCs are provided.

Unveiling Crystal Structure Landscapes and Morphology Modification Rules of Substituted Benzophenone Crystals

Unveiling Crystal Structure Landscapes and Morphology Modification Rules of Substituted Benzophenone Crystals

Radiofrequency affects the decrystallization efficiency and physicochemical properties of rape honey via crystal structure modification and inactivating enzyme

Crystallization degrades the physicochemical properties of honey and reduces consumer acceptance. To address this issue, radiofrequency was developed to investigate the decrystallization efficiency and quality impact mechanism of rape honey. The results showed that radiofrequency significantly decreased the number and size of crystals, leading to shortening the decrystallization time to less than 10 min. The response surface optimization methodology further indicated that the highest decrystallization rate (98.72 ± 0.34 %) and lower 5-Hydroxymethylfurfural (2.45 ± 0.12 mg/kg) contents were obtained. Furthermore, radiofrequency changed the honey from a pseudoplastic into a Newtonian fluid efficiently due to the volumetric heating feature. It is worth noting that the inactivation of glucose oxidase reduced the antibacterial capacity, while the increase in total phenolic and flavonoid contents improved the antioxidant capacity of rape honey. In summary, current findings indicated that radiofrequency is a potential alternative decrystallization technology for water baths.

Effect of laser power density on formation of oxide particles during ablation of metallic bismuth in atmospheric air

Purposeful synthesis of bismuth oxide nanoparticles (NPs) of various crystal modifications is important for biomedicine, photocatalysis and other applications. In this work, pulsed laser ablation of a metallic Bi target in atmospheric air is used to obtain β-Bi2O3 NPs. The effect of the Nd:YAG laser radiation power density (1064 nm, 7 ns) in the range of 0.1–1.2 GW/cm2 on the features of formation of NPs under nonequilibrium conditions is studied, for which the spectra of laser-induced plasma are recorded and analyzed, the plasma composition is determined, and the temperature of the plasma plume is estimated. The NPs are comprehensively characterized using TEM, XRD, FTIR, Raman, and UV–Vis spectroscopies, and electrophoretic light scattering, which make it possible to determine their morphology, crystal structure, chemical composition, and optical properties. The photocatalytic activity of the resulting nanopowders in the Rhodamine B dye decomposition reaction is assessed.

In-Situ Raman Spectroscopy of Li+ and Na+ Storage in Anodic Nanotubes

Anodizing is a high-voltage electrochemical conversion process that forms barrier-type oxide layers or self-organized nanoporous/nanotubular structures. So far, the Al2O3-like nanopores and TiO2-like nanotubes could be successfully synthesized on many valve metals and alloys.Recently, it become possible to form nanotubular structures on iron and consequently control the ratio of hematite (Fe2O3) to magnetite (Fe3O4) by subsequent thermal treatment.1 Electrochemically active nanotubes, such as self-organized TiO2 are of high interest in the battery field due to a unique one-dimensional (1D) geometry offering high volume expansion tolerance and applications without binders and conductive additives. Herein, we report an in - situ Raman spectroscopy study under current control for a better fundamental understanding of Li+/Na+ storage in nanotubes and correlate the structural fingerprints with the electrochemical data on differential capacity plots of d(Q–Q 0) dE –1.2 Real-time measurements revealed that the nanotubes had undergone two major phase transformations with increasing lithium content, disclosing the sequential steps of a lithium intercalation type of storage. In contrast, sodium-ion insertion induced no significant crystal structure modification but instead a slight crystallinity rupture, signifying a dominant nondiffusion-limited capacitive type of storage. The insight into the charge storage in a 1D material in relation to other nanostructures such as nanoparticles3 will be discussed.1. L. Fadillah, D. Kowalski, M. Vincent, C. Zhu, S. Kitano, Y. Aoki and H. Habazaki, ACS Applied Materials & Interfaces , 2023, 15, 52563-52570.2. M. Vincent and D. Kowalski, ACS Applied Nano Materials , 2023, 6, 6528-6537.3. M. Vincent, S. S. Kumar and D. Kowalski, Electrochimica Acta , 2023, 469, 143161. Figure 1

Oxygen-defect rich SnO2-based homogenous composites for fast response and recovery hydrogen sensor

As a kind of green energy, hydrogen (H2) has been widely concerned and applied by people. One of the biggest challenges for sensing applications is the quick detection of hydrogen leaks or their release in various conditions, particularly in large electric vehicle batteries. This study successfully constructed a quick response and recovery hydrogen sensor based on the In2O3-SnO2 heterojunction. The response and recovery time of the In2O3-SnO2 hydrogen sensor is 1.1/1.9 s to 50 ppm H2. This is reduced to 11.0 %/9.5 % compared to the SnO2 hydrogen sensor. This sensor's remarkable gas detecting properties are mainly attributed to the In2O3-SnO2 heterojunction creation, crystal structure modification, and increased specific surface area (92.9 m2/g). Homogenous In2O3-SnO2 nanocomposites contain more oxygen defects, which is the primary factor enhancing the sensor's ability to detect gases. Firstly, indium ions are incorporated in the lattice of SnO2 results in lattice distortion and enhances the presence of oxygen deficiency in the composites, which plays a pivotal role in achieving rapid response and recovery of the sensor. Secondly, In2O3-SnO2 heterostructures promote rapid adsorption of oxygen molecules and target gases by facilitating effective electron mobility on their surface. The quicker response and recovery times of hydrogen sensors based on In2O3-SnO2 heterojunctions are observed. This innovative approach to creating fast-responding gas sensors highlights the promise of heterojunction-based hydrogen sensors for real-time H2 monitoring and opens up new research directions.

Photoelectrocatalytic Hydrogen Generation: Current Advances in Materials and Operando Characterization.

Photoelectrochemical (PEC) hydrogen generation is a promising technology for green hydrogen production yet faces difficulties in achieving stability and efficiency. The scientific community is pushing toward the development of new electrode materials and a better understanding of the underlying reactions and degradation mechanisms. Advances in photocatalytic materials are being pursued through the development of heterojunctions, tailored crystal nanostructures, doping, and modification of solid-solid and solid-electrolyte interfaces. Operando and in situ techniques are utilized to deconvolute the charge transfer mechanisms and degradation pathways. In this review, both materials development and Operando characterization are covered for advancing PEC technologies. The recent advances made in the PEC materials are first reviewed including the applied improvement strategies for transition metal oxides, nitrites, chalcogenides, Si, and group III-V semiconductor materials. The efficiency, stability, scalability, and electrical conductivity of the aforementioned materials along with the improvement strategies are compared. Next, the Operando characterization methods and cite selected studies applied for PEC electrodes are described. Operando studies are very successful in elucidating the reaction mechanisms, degradation pathways, and charge transfer phenomena in PEC electrodes. Finally, the standing challenges and the potential opportunities are discussed by providing recommendations for designing more efficient and electrochemically stable PEC electrodes.

Nb/Mn co‐doping enhances the pyroelectric properties of Na0.5Bi4.5Ti4O15 ceramics for infrared detection

AbstractThe pyroelectric effect has wide applications in various fields, such as infrared imaging, detection, alarms, and the expanding field of smart homes. The rapid advancement of smart systems, focusing on miniaturization and integration, requires pyroelectric infrared detectors with high pyroelectric coefficients and Curie temperatures to meet the requirements of integrated processes. However, the Curie temperature of commercial lead zirconate titanate is limited to <230°C, urgently looking for a breakthrough. Here, we explore pyroelectricity in Na0.5Bi4.5Ti4O15 (NBT) ceramics, characterized by a high Curie temperature (∼660°C). We systematically examined the crystal structure modifications and defect dipole effects of the Nb/Mn‐co‐doped NBT. The lattice expansion, distortion of the TiO6 octahedra, and structural transformation tendency from the orthorhombic to tetragonal phase facilitate dipole movements with increasing temperature. Furthermore, the Mn and Nb elements result in the formation of MnTi“–VO·· and NbTi·–MnTi” –NbTi· defect dipoles, inducing additional polarization changes in response to temperature variations. Finally, a significantly improved pyroelectric coefficient of 110 µC m2 K–1 and remarkable temperature stability from 25°C to 300°C is achieved in NBTM‐5Nb ceramics. This co‐doping strategy for enhancing pyroelectric performance can be expanded to other systems and substantially contribute to advancing high‐performance materials for infrared detection.

Development of CaCO3 novel morphology through crystal lattice modification assisted by sulfate incorporation and vibration

CaCO3 has long been used as a filler to increase many properties of the material. The filler commonly consists of inexpensive materials that replace some volume of the more expensive materials, which can reduce the cost of the final product. CaCO3 morphology that can be used as filler depends on the filler's function, such as filler for paper, paint, rubber, or composite. A filler for composite materials is needed to increase interfacing interactions between the particulate fillers and the matrix. So, the particulate in a broader shape will be the best choice to function for such filler. In this research, in an attempt to increase the interfacing interaction, CaCO3 morphology was modified in such a way through crystal lattice modification assisted by sulfate incorporation and vibration. SEM analysis was implemented, and showed that the research successfully produced novel morphology in branchy-like polymorphs. FTIR analysis also proved that the crystal lattice has been modified. The morphology in branchy-like polymorph is supposed to increase interfacing interaction between CaCO3 as the filler and the matrix. The methods are also supposed to be implemented as the research is scaled up to commercial scale.

Nanomaterials as Next-Gen Corrosion Inhibitors: A Comprehensive Review for Ceramic Wastewater Treatment

This study reviews the use of corrosion inhibitors in industrial wastewater treatment, specifically in ceramic wastewater. It discusses the main problem limits the use of treated wastewater, which is corrosion behavior. To reduce this behavior and enable safe reuse of industrial wastewater, corrosion inhibitors are used. The study aims to provide insights into the selection, use, and effectiveness of corrosion inhibitor types in the media under study. The results can help engineers, researchers, and wastewater treatment professionals to find the best corrosion inhibitors for various municipal wastewater applications, increasing the sustainability and efficiency of wastewater treatment processes. The ceramic industry faces challenges in managing complex aqueous effluents generated from mining, shaping, glazing, and manufacturing processes. Nanomaterial-based alternatives, such as titanium nanotubes, zinc oxide nanoparticles, nanoenhanced filters, and stimuli responsive polymer and silica coatings, have emerged as promising next-generation corrosion inhibitors due to their multilayer passivation and high specific surface area. The analysis focuses on the feasibility of these materials' mechanisms, such as crystal deformation, nucleation hindrance, coating barriers, and passivation improvement, in industrial settings. In conclusion, the use of corrosion inhibitors in industrial wastewater treatment can significantly improve the sustainability and efficiency of wastewater treatment processes. Understanding the mechanisms by which these nanomaterials influence crystal growth modification, deposition kinetics, and passivation performance could lead to more effective and sustainable solutions for industrial wastewater treatment.

Critical Role of Cu Nanoparticle-Loaded Cu(100) Surface Structures on Structured Copper-Based Catalysts in Boosting Ethanol Generation in CO2 Electroreduction.

Presently, realizing high ethanol selectivity in CO2 electroreduction remains challenging due to difficult C-C coupling and fierce product competition. In this work, we report an innovative approach for improving the efficiency of Cu-based electrocatalysts in ethanol generation from electrocatalytic CO2 reduction using a crystal plane modification strategy. These novel Cu-based electrocatalysts were fabricated by electrochemically activating three-dimensional (3D) flower-like CuO micro/nanostructures grown in situ on copper foils and modifying with surfactants. It was demonstrated that the fabricated Cu-based electrocatalyst featured a predominantly exposed Cu(100) surface loaded with high-density Cu nanoparticles (NPs). The optimal Cu-based electrocatalyst displayed considerably improved CO2 electroreduction performance, with a Faraday efficiency of 37.9% for ethanol and a maximum Faraday efficiency of 68.0% for C2+ products at -1.4 V vs RHE in an H-cell, accompanied by a high current density of 69.9 mA·cm-2, much better than the particulate Cu-based electrocatalyst. It was unveiled that the Cu(100)-rich surface of nanoscale petals with abundant under-coordinated copper atoms from CuNPs was conducive to the formation and stabilization of key *CH3CHO and *OC2H5 intermediates, thereby promoting ethanol generation. This study highlighted the critical role of CuNP-loaded Cu(100) surface structures on structured Cu-based electrocatalysts in enhancing ethanol production for the CO2 electroreduction process.

Enhanced High Voltage Stability of Spinel‐Type Structured LiNi0.5Mn1.5O4 Electrodes: Targeted Octahedral Crystal Site Modification

AbstractHigh‐voltage spinel‐type structured LiNi0.5Mn1.5O4 (LNMO) shows promise as a next‐generation high‐energy‐density lithium‐ion battery cathode material, however, capacity decay on extended cycling hinders its widespread adoption, underscoring an urgent need for further development. In this work, we introduce Zn at octahedral 16c crystal sites in LNMO with Fd m space group to improve rate capability and reduce the rapid capacity decay otherwise experienced during extended cycling. The current work resolves the detailed influence of isolated modification at octahedral 16c crystal sites, unveiling the mechanism for these performance improvements. We show that occupation of Zn at previously empty 16c sites prevents the migration of Ni/Mn to adjacent 16c sites, eliminating transformation to a rock‐salt type structured Ni0.25Mn0.75O2 phase above 4.8 V, preventing structure degradation and suppressing voltage polarization. This study provides insights into the fundamental structure‐function relationship of the LNMO battery cathode, pointing to pathways for the crystal structure engineering of materials with superior performance.

The study of the structure and performance of polyoxymethylene modified by nucleating agent L

With the expanding application areas of polyoxymethylene (POM), the challenges in its crystal modification are becoming greater. Conventional nucleating agents have issues with compatibility with POM. So we used a nucleating agent L with a similar molecular chain structure to POM through melt blending to modify POM. Using instruments to characterize and test the samples, and studying the effect of nucleating agent L on the structure and properties of POM. The results showed that after adding a small amount of nucleating agent. The crystal size was reduced. The number and size of micro-pores at the cross-section were significantly reduced. The crystallization performance of POM were improved. This provides a new direction for the future development of POM-specific nucleating agents and the direction of efficient nucleating.

Crystal Structure Modification and Dielectric Properties of Sr- and La-Containing A2B2O7 Thin Films for High-Temperature Operational Film Capacitors.

In order to obtain thermally stable thin-film materials with high dielectric constant, A2B2O7 thin films (Sr2Ta2O7, Sr2Nb2O7, La2Zr2O7, and La2Ti2O7) containing Sr or La and their solid solutions were grown on Pt/Ti/SiO2/Si substrates by RF sputtering and their crystal structures and dielectric properties were investigated. The Sr2Ta2O7 and La2Ti2O7 films exhibit highly oriented crystal structures. By contrast, the Sr2Nb2O7 and La2Zr2O7 films exhibit polycrystalline structures. The leakage properties of the Sr-containing films are lower and more stable in the high-temperature region (up to 300 °C) than those of the La-containing films. Among the investigated films, the Sr2Ta2O7 film grown at 500 °C and annealed at 900 °C shows the most stable dielectric constant with respect to temperature in the temperature range from room temperature to 300 °C. In addition, the xSr2Ta2O7-(1-x)La2Ti2O7 solid solutions exhibit enhanced dielectric properties at x = 0.35. The dielectric constant is greater than 100, and its variation with temperature is less than 10%. The Sr-containing A2B2O7 ferroelectric thin films have potential applications as high-temperature film capacitors that can operate at temperatures as high as 300 °C.

The potential of sonocrystallization in crystal habit modification for improving micromeritic and physicochemical properties of Dapagliflozin

Dapagliflozin propanediol monohydrate (DAPA), an antidiabetic drug owing to its needle-shaped crystals exhibits poor micromeritic and physicochemical properties. Crystal habit modification by conventional and sonocrystallization approaches was employed to improve its manufacturability. SEM analysis of sonocrystallized DAPA in acetonitrile (DAPA_SNC3) revealed a rod habit with lower aspect ratio (3.56±0.91) and narrow size distribution (span value-1.37). In case of DAPA_EH and DAPA_CS (solvent evaporation in ethanol:n-hexane, and chloroform, respectively), rod and plate-shaped crystals were obtained with aspect ratios 6.98±5.84 and 6.03±4.21, respectively. All three samples showed significantly improved powder flowability (p<0.0001) compared to DAPA. Further solid-state characterization by FTIR, TGA, DSC, and PXRD showed no polymorphic changes in recrystallized samples. The contact angle studies in water revealed wetting tendency in the following order: SONO_SNC3>SONO_EH>SONO_CS>DAPA. Polar energies of DAPA_SNC3 and DAPA_CS were significantly higher (p<0.01 & p<0.001, respectively) when compared with DAPA. The XPS studies showed increased hydrophilic elements on the surfaces of DAPA_SNC3 crystals which resulted in improved wettability. DAPA_SNC3 among all samples showed highest tensile strength at 200 MPa compression force because of its shape. DAPA_EH showed no significant improvement in IDR profile, while DAPA_CS and DAPA_SNC3 showed significantly faster IDR because of prominent polar functionality (p<0.05 and p<0.0001, respectively).

Effect of carboxymethyl chitosan on the storage stability of rice dough during frozen storage

In this study, we aimed to determine the effect of carboxymethyl chitosan (CMCh) and carboxymethyl cellulose sodium (CMCNa) on the quality of frozen rice dough. We used a variety of methods to conduct a thorough investigation of frozen rice dough, including nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, size exclusion high-performance liquid chromatography (SE-HPLC), X-ray diffraction (X-RD), differential scanning calorimetry (DSC), and rapid visco analyzer (RVA). Our findings showed that frozen storage caused significant damage to the texture of rice dough, and this damage was reduced by the inclusion of CMCh, which led to a gradual change in the orderly structure of proteins. The degree of cross-linking between CMCh-B (DS:1; 0.5 %, 1 %, and 1.5 %) and the large protein polymer was significantly higher than that between CMCh-A (DS:0.8; 0.5 %, 1 %, and 1.5 %) and CMCNa (DS:1; 1 %), which decreased the ability of bound water to become free water. This resulted in the increase of tan δ, which effectively delayed the structural transformation of frozen rice dough. Furthermore, the introduction of CMCh delayed the immediate order of starch and crystal structure modifications, altering the thermal properties and pasting qualities of the frozen rice dough. Therefore, 1.5 % CMCh-B showed the best protective effect on frozen rice dough.

Tailoring surface defects to enhance PBX surface adhesion through autologous surface molecular reconfiguration

Surface modification of explosive crystals is crucial for enhancing the performance of explosives, particularly polymer-bonded explosives (PBXs). Traditional methods to boost mechanical properties in PBXs, such as surface coating, often encounter issues like complex operations, inadequate adhesion, and impurity introduction. In this paper, direct surface modification via the assembly-disassembly of NH…O hydrogen bond synthon was presented for enhancing interfacial adhesion. Using the autologous surface molecular reconfiguration resulting from hydrogen bond synthon, diverse surface defects were introduced on crystals. The notable surface alterations are influenced by concentration and suspension time. The crystal surface with irregular surface morphology adheres more strongly to the binders and its PBXs were increased the elastic recovery by 28.9 % compared to the raw material. Furthermore, this technique of altering crystal surface properties by introducing surface defects not only maintains the purity of the particles but simplifies the preparation process, making it efficient and environmentally friendly.

New Improved cGMP Analogues to Target Rod Photoreceptor Degeneration.

Retinitis pigmentosa (RP) is a form of retinal degeneration affecting a young population with an unmet medical need. Photoreceptor degeneration has been associated with increased guanosine 3',5'-cyclic monophosphate (cGMP), which reaches toxic levels for photoreceptors. Therefore, inhibitory cGMP analogues attract interest for RP treatments. Here we present the synthesis of dithio-CN03, a phosphorodithioate analogue of cGMP, prepared using the H-phosphonothioate route. Two crystal modifications were identified as a trihydrate and a tetrahydrofuran monosolvates. Dithio-CN03 featured a lower aqueous solubility than its RP-phosphorothioate counterpart CN03, a drug candidate, and this characteristic might be favorable for sustained-release formulations aimed at retinal delivery. Dithio-CN03 was tested in vitro for its neuroprotective effects in photoreceptor models of RP. The comparison of dithio-CN03 to CN03 and its diastereomer SP-CN03, and to their phosphate derivative oxo-CN03 identifies dithio-CN03 as the compound with the highest efficacy in neuroprotection and thus as a promising new candidate for the treatment of RP.

Improvement of Flow Properties of Highly Waxy Crude Oil with the application of SiO2 and Graphene Oxide nanoparticles aided by Light Crude Oil

The rheological behaviour of crude oil mixtures comprising both heavy and light components along with chemical additives is of significant interest due to its relevance in the petroleum industry. Understanding the flow properties of these mixtures is crucial for efficient transportation, processing, and refining operations. This study investigates the effectiveness of incorporating light crude oil and nanoparticles as additives to mitigate wax-related flow issues. The test involves six different waxy/heavy and light crude oil mixture concentrations along with Graphene Oxide and Silicon Dioxide nanoparticles. Rheological tests were conducted to evaluate the impact of these additives on the flow behaviour of waxy crude oil. The rheological characterization involved measuring the viscosity, yield stress, and shear rate dependencies of waxy crude oil samples with varying concentrations of light crude oil and nanoparticles. Nano-materials have emerged as promising candidates for mitigating wax deposition issues and enhancing the fluidity of crude oil. Nevertheless, the intricate nature of crude oil has made it challenging to elucidate the underlying mechanisms governing wax resolution, crystal modification, and flow improvement. The results revealed notable improvements in the rheological properties of the treated crude oil, including reduced viscosity and enhanced flowability, even at low temperatures. The incorporation of light crude oil and nanoparticles proved to be a promising strategy for modifying the rheological behaviour of waxy crude oil, ensuring improved flow assurance. This study contributes to understanding innovative approaches to address flow challenges in waxy crude oil systems, thereby offering potential solutions for the oil and gas industry.

High content pyridine nitrogen-doped carbon nanosheets derived from ZIF-L as anode materials of lithium-ion batteries with excellent capacity and rate performance

The precise control of nitrogen doping types in carbon materials is crucial for optimizing energy storage devices. In this study, we synthesize nitrogen-doped carbon nanosheets (NCS) using ZIF-L as a precursor. Comparatively, the two-dimensional crystal structure of ZIF-L provides several advantages over ZIF-8 as a precursor in terms of nitrogen doping efficiency, achieving a higher doping level (14.56 %) and an increased ratio of pyridinic nitrogen (53.60 %). Consequently, NCS display a greater capacity for pseudocapacitive lithium storage. Furthermore, by adjusting the carbonization temperature, we precisely tailor the graphite-nitrogen doping level of NCS within the range of 16.80–31.22 %. Remarkably, when employed as an anode material in lithium-ion batteries, NCS-800 demonstrates exceptional cycling stability, with a capacity retention of 1078 mAh g−1 after 500 cycles at a current density of 0.5 A g−1, as well as excellent rate capability (735 mAh g−1 at 5 A g−1). This study not only compares the impact of precursor crystal structure modifications on nitrogen doping and lithium storage performance but also introduces a novel synthesis methodology for highly nitrogen-doped carbon materials, offering new avenues for future research in this field.