Traditional Synthesis Research Articles

High‐throughput combinatorial approach expedites the synthesis of a lead‐free relaxor ferroelectric system

AbstractDeveloping novel lead‐free ferroelectric materials is crucial for next‐generation microelectronic technologies that are energy efficient and environment friendly. However, materials discovery and property optimization are typically time‐consuming due to the limited throughput of traditional synthesis methods. In this work, we use a high‐throughput combinatorial synthesis approach to fabricate lead‐free ferroelectric superlattices and solid solutions of (Ba0.7Ca0.3)TiO3 (BCT) and Ba(Zr0.2Ti0.8)O3 (BZT) phases with continuous variation of composition and layer thickness. High‐resolution x‐ray diffraction (XRD) and analytical scanning transmission electron microscopy (STEM) demonstrate high film quality and well‐controlled compositional gradients. Ferroelectric and dielectric property measurements identify the “optimal property point” achieved at the composition of 48BZT–52BCT. Displacement vector maps reveal that ferroelectric domain sizes are tunable by varying {BCT–BZT}N superlattice geometry. This high‐throughput synthesis approach can be applied to many other material systems to expedite new materials discovery and properties optimization, allowing for the exploration of a large area of phase space within a single growth.image

Continuous tuning of optical transition properties and phonon spectrum in Er3+ doped germano-tellurite glass system

With the development of science and the progress of technology, novel and advanced rare earth ions doped luminescent materials with higher performance are demanded in the both emerging and traditional applications. Understanding the rules for tuning the spectroscopic properties of these materials is crucial for their development. However, achieving precise control over the optical properties of rare earth doped materials using traditional design and synthesis methods, such as altering dopants and their concentrations or modifying the preparative conditions, still remains challenging. This work aims to adjust the optical transition characteristics of Er3+ doped germano-tellurite glasses by changing the glass components. First, the Er3+ doped germano-tellurite glass series were synthesized using a high-temperature melt-quenching method at optimized melting temperatures. The tuning of band gap energy and refractive index of the glasses were revealed, and it was found that both of them can be monotonically and continuously tuned by changing the glass composition. The optical transition intensity parameters of Er3+ in the glasses were calculated in the framework of traditional three-parameterized Judd-Ofelt theory using the absorption spectra, and furthermore the corresponding optical transition parameters including radiative transition rates and intrinsic lifetimes for some interested levels were alsoconfirmed. The results demonstrated that the optical transition parameters could be efficiently modulated by changing the glass composition, indicating that the spectral properties of Er3+ doped germano-tellurite glasses can be tuned for the practical applications. The reliability of the deduced tuning rule was validated by comparing the theoretical and experimental transition rate ratios of 2H11/2 → 4I15/2 to 4S3/2 → 4I15/2. Furthermore, the tuning regulation of the phonon spectra in relation to the glass composition was discovered, showing a concordance between theoretical predictions and experimental results. From the above facts, it can be concluded that the optical transition properties of Er3+ in germano-tellurite glasses can be substantially adjusted by modifying the glass composition. This work provides a new perspective for designing and developing novel luminescent materials to meet specific application needs.

Universal integration of photothermal particles onto g-C3N4 towards improved photocatalysis

The photothermal effect has been recognized as a universal promoter in various photocatalytic reactions. However, in many promising nanocomposite systems, the integration of heterogeneous photothermal materials with photocatalysts remains a significant technical challenge. Focusing on the emerging graphitic carbon nitride (g-C3N4) based photocatalyst, we identified that the segregation of the introduced photothermal particles results from the dynamic instability of the original solid-solid dispersion system, which essentially origins from a sluggish two-step solid-liquid-solid phase transformation of urea towards g-C3N4. By taking advantages of the photothermal particles to be loaded, we developed a photothermal-polymerization strategy to create a rapid heating to overcome their undesired segregation during g-C3N4 formation. The strategy enables a one-step loading of various photothermal particles on the g-C3N4, presenting a versatile methodology. This sustainable technique enhances the synthesis yield of g-C3N4 by 352 % with reduced energy consumption. The derived photothermal particles-dispersed g-C3N4 shows 290 % improvement in photocatalytic CO2 reduction compared to the separated system, which is obtained from the traditional heating synthesis. Beyond enriching the accessible categories of composite catalysts, this study may deepen physiochemical insights into the dynamic transformation of the novel dispersion system.

Functionalization of 1,3‐Butadiene Derivatives under Photo/Electrocatalysis

AbstractIn recent years, the functionalization of 1,3‐butadiene has become an attractive strategy for constructing allyl compounds with molecular and structural complexity, and the current research focuses on synthetic chemistry and organic synthesis. Compared with the traditional synthesis method, the synthesis methods promoted by photochemistry or electrochemistry represent an environmentally friendly and mild strategy. In this review, the functionalization reactions of 1,3‐butadiene under photochemical/electrochemical processes in recent years are reviewed according to the classification of functionalization systems, with particular emphasis on the corresponding reaction mechanism, which lays a foundation for further exploration of new catalytic methods.

An improved image texture synthesis based on algorithm convolution neural network

In recent years, texture synthesis technology has made great progress and has become one of the research hotspots in the fields of computer graphics, computer vision and image processing. Texture synthesis is proposed to solve problems such as seam aliasing in texture mapping. With the development of artificial intelligence technology, texture synthesis methods can achieve more effective results. Therefore, this paper improves the traditional texture synthesis method based on convolutional neural network. By using the VGGnet network model of the convolutional neural network and adding the Batch Normalization (BN) layer to individual convolutional layer affiliated to the network, the network training speed is improved. In this paper, the source texture image and an image initialized by white noise are respectively input into the convolutional neural network. After the forward propagation process, the texture features of the images are extracted, the loss function is constructed, and then the network is trained to update the composite image. Extensive results of experiments indicate that our proposed approach outperforms other texture synthesis methods in terms of image synthesis quality.

Pilot Induced Oscillations of the Small Unmanned Aerial Vehicles

Abstract The unintentional inputs of the UAV operators in certain conditions might lead to the unwanted, pilot induced oscillations (PiO) of the aircraft. The PiOs might cause severe damages of the UAV, or as the worth, might lead to the loss of the aircraft. The PiOs of the manned aircraft are in the focus of attention for many decades. However, the PiOs of the UAVs became an important issue worth to investigate only in the past few years. Thus, scientific results and proven statements gained in this field might enrich both the on-going UAV operator training programs and UAV autopilot design based mostly on traditional synthesis methods and procedures.

Green synthesis and applications of mono/bimetallic nanoparticles on mesoporous clay: a review

Abstract Green nanotechnology comprises the use of natural sources such as plant extracts as both reducing and stabilizing agents thereby reducing the reliance on hazardous chemicals. Recent breakthroughs in nanotechnology involve the incorporation of various metals to create mono and bimetallic nanoparticles, catalyzing transformative shifts. However, concerns arise due to the environmental impact of traditional synthesis methods. An alternative approach focuses on biosynthesized metal nanoparticles using clay, specifically Bentonite, MMT (Montmorillonite) and Kaolinite as supportive materials, emphasizing the prevention of agglomeration with clay and the use of plant extracts. The integration of clay, especially Bentonite, MMT and Kaolinite enhances the stability and functionality. The review emphasizes mitigating environmental impact by reducing metal ions and explores the use of phytochemicals fro environmentally friendly nanoparticle synthesis. Incorporating clay minerals not only improves synthesis efficiency but also minimizes the ecological footprint. Future research is expected to focus on integrative approaches in plant nanotechnology, particularly in agriculture and broader plant science. The comprehensive review covers literature from 2015 to 2023, providing systematic and interpretative data, highlighting progress and potential in eco-friendly metal nanoparticles synthesis supported on clay minerals.

Lower-Temperature Nucleation and Growth of Colloidal CdTe Quantum Dots Enabled by Prenucleation Clusters with Cd-Te Bond Conservation.

The reason why heating is required remains elusive for the traditional synthesis of colloidal semiconductor quantum dots (QDs) of II-VI metal chalcogenide (ME). Using CdTe as a model system, we show that the formation of Cd-Te covalent bonds with individual Cd- and Te-containing compounds can be decoupled from the nucleation and growth of CdTe QDs. Prepared at an elevated temperature, a prenucleation-stage sample contains clusters that are the precursor compound (PC) of magic-size clusters (MSCs); the Cd-Te bond formation occurs at temperatures higher than 120 °C in the reaction. Afterward, the PC-to-QD transformation appears via monomers at lower temperatures in dispersion. Our findings suggest that the number of Cd-Te bonds broken in the PC reactant is similar to that of Cd-Te bonds formed in the QD product. For the traditional synthesis of ME QDs, heating is responsible for the M-E bond formation rather than for nucleation.

Mechanism of Nitrone Formation by a Flavin-Dependent Monooxygenase.

OxaD is a flavin-dependent monooxygenase (FMO) responsible for catalyzing the oxidation of an indole nitrogen atom, resulting in the formation of a nitrone. Nitrones serve as versatile intermediates in complex syntheses, including challenging reactions like cycloadditions. Traditional organic synthesis methods often yield limited results and involve environmentally harmful chemicals. Therefore, the enzymatic synthesis of nitrone-containing compounds holds promise for more sustainable industrial processes. In this study, we explored the catalytic mechanism of OxaD using a combination of steady-state and rapid-reaction kinetics, site-directed mutagenesis, spectroscopy, and structural modeling. Our investigations showed that OxaD catalyzes two oxidations of the indole nitrogen of roquefortine C, ultimately yielding roquefortine L. The reductive-half reaction analysis indicated that OxaD rapidly undergoes reduction and follows a "cautious" flavin reduction mechanism by requiring substrate binding before reduction can take place. This characteristic places OxaD in class A of the FMO family, a classification supported by a structural model featuring a single Rossmann nucleotide binding domain and a glutathione reductase fold. Furthermore, our spectroscopic analysis unveiled both enzyme-substrate and enzyme-intermediate complexes. Our analysis of the oxidative-half reaction suggests that the flavin dehydration step is the slow step in the catalytic cycle. Finally, through mutagenesis of the conserved D63 residue, we demonstrated its role in flavin motion and product oxygenation. Based on our findings, we propose a catalytic mechanism for OxaD and provide insights into the active site architecture within class A FMOs.

Rapid Hydrolysis Precipitation of BiOBr Nanosheets for Boosting Photocatalytic N2 Fixation

AbstractIn this paper, BiOBr nanosheets were synthesized through a novel hydrolysis precipitation method, which significantly reduced energy consumption and time cost compared to traditional hydrothermal synthesis methods. The subjected hydrothermal and high‐temperature calcination process promote the generation of surface oxygen vacancies, which inhibited the recombination of photogenerated electron hole pairs and improve the photocatalytic performance of BiOBr. Additionally, by adjusting the addition amount of KOH in the synthesis process, BiOBr can grow towards more complex crystal structure, which also provides a new path for the fabrication of 2D materials.

Boosting Up Electrosynthesis of Urea with Nitrate and Carbon Dioxide via Synergistic Effect of Metallic Iron Cluster and Single-Atom.

Electrocatalytic conversion of nitrates and carbon dioxide to urea under ambient conditions shows promise as a potential substitute for traditional urea synthesis processes characterized by high consumption and pollution. In this study, a straightforward one-pot method is employed to prepare a highly efficient FeNC-Fe1N4 electrocatalyst, consisting of atomically dispersed Fe1N4 sites and metallic Fe clusters (FeNC) with particle size of 4-7nm. The FeNC-Fe1N4 catalyst exhibits remarkable electrocatalytic activity for urea synthesis from nitrate anion (NO3 -) and carbon dioxide (CO2), achieving a urea production rate of 38.2mmolgcat -1h-1 at -0.9V (vs RHE) and a Faradaic efficiency of 66.5% at -0.6V (vs RHE). Both experimental and theoretical results conclusively demonstrate that metallic Fe clusters and Fe1N4 species provide active sites for the adsorption and activation of NO3 - and CO2, respectively, and the synergistic effect between Fe1N4 and metallic Fe clusters significantly enhances the electrochemical efficiency of urea synthesis. In all, this work contributes to the rational design and comprehensive synthesis of a dual-active site iron-based electrocatalyst, facilitating efficient and sustainable urea synthesis.

Interface engineering of 2D NiFe LDH/NiFeS heterostructure for highly efficient 5-hydroxymethylfurfural electrooxidation

The electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to valuable chemicals is an efficient way to upgrade biomass molecules and replace traditional catalytic synthesis. It is crucial to develop efficient and low-cost earth-abundant electrocatalysts to enhance catalytic performance of HMF oxidation. Herein, a new type of two-dimensional (2D) hybrid arrays consisting of NiFe layered double hydroxides (LDH) nanosheets and bimetallic sulfide (NiFeS) is constructed via interface engineering for efficient electrocatalytic oxidation of HMF to 2,5-furandicarboxylic acid (FDCA). The preparation process of 2D NiFe LDH/NiFeS with ultrathin heterostructure involves in anchoring a Co-based metal-organic framework (Co MOF) as template onto the carbon cloth (CC) via in-situ growth, formation of NiFe LDH on the surface of Co MOF and subsequent partial sulfidation. The electrocatalyst of NiFe LDH/NiFeS exhibits outstanding performance towards HMF oxidation, about 98.5% yield for FDCA and 97.2% Faraday efficiency (FE) in the alkaline electrolyte with 10 mmol/L HMF, as well as excellent stability retaining 90.1% FE for FDCA after six cycles test. Moreover, even at an HMF concentration of 100 mmol/L, the yield and FE for FDCA remain high at 83.6% and 93.6%, respectively. These findings highlight that 2D heterostructure containing abundant interfaces between NiFe LDH nanosheets and NiFeS can enhance the intrinsic activity of LDH and thus promote the oxidation reaction kinetics. Additionally, the synergistic effect of the bimetallic NiFe compounds also improved the selectivity of HMF conversion to FDCA. Our present work demonstrates that constructing 2D ultrathin heterostructure of NiFe LDH/NiFeS is a facile strategy via interface engineering to enhance the intrinsic activity of LDH electrocatalysts, which would open new avenues toward low-cost and advanced 2D nanocatalysts for sustainable energy conversion and electrochemical valorization of biomass derivatives.

Synergistic Photoenzymatic Catalysis Enables Synthesis of a-Tertiary Amino Acids Using Threonine Aldolases.

a-Tertiary amino acids are essential components of drugs and agrochemicals, yet traditional syntheses are step-intensive and provide access to a limited range of structures with varying levels of enantioselectivity. Here, we report the α-alkylation of unprotected alanine and glycine by pyridinium salts using pyridoxal (PLP)-dependent threonine aldolases with a Rose Bengal photoredox catalyst. The strategy efficiently prepares various a-tertiary amino acids in a single chemical step as a single enantiomer. UV-vis spectroscopy studies reveal a ternary interaction between the pyridinium salt, protein, and photocatalyst, which we hypothesize is responsible for localizing radical formation to the active site. This method highlights the opportunity for combining photoredox catalysts with enzymes to reveal new catalytic functions for known enzymes.

A review of flame aerosol synthesis technology for the synthesis of nanoparticles and functional energy materials

The outstanding performance of nanomaterials in chemical, magnetic, electrical, catalytic, and mechanical properties has paved the way for the huge market in material fabrication, energy storage, electronics, and many other industries. Traditional synthesis methods are relatively stunted in industrial applicability and scalability due to complex manufacturing processes and long preparation times, hampering the development and commercialisation of nanomaterials. On the other hand, the flame synthesis method emerges as an inexpensive, efficient, and easily scalable method for the commercial production of nanoparticles. The present review aims to highlight the research status and applications of the nanomaterials synthesised by the flame aerosol method. The advancement of flame aerosol synthesis technologies is reviewed, with emphasis on the state-of-the-art flame reactor configuration and design. Critical flame parameters that govern the formation of nanoparticles in the flame are reviewed to provide an understanding of the formation criteria and growth of nanomaterials in the flame environment. The properties and characteristics of carbon-based, platinum group metal, metal oxide, bimetallic nanoparticles, perovskite and high entropy oxide nanomaterials produced by flame synthesis are extensively reviewed. In addition, commercial manufacturing of flame-synthesised materials along with applications of the nanomaterials in the field of thermal or photocatalytic energy storage, fuel cells, and gas sensing are presented.

Unveiling kinetics post rate-determining step in Brønsted acid-catalyzed reactions of fructose: A strategy for 5-hydroxymethylfurfural production from concentrated feedstock

The development of high-yielding catalytic systems is pivotal in biomass upgrading. However, the investigation of kinetics in these complex reaction systems is often highly challenging, especially when reactions leading to byproduct formation are obscured by a preceding, slow rate-determining step. In this work, we introduce a unique approach to kinetic analysis that enables the investigation of reactions occurring post rate-determining step. The technique was applied to the conversion of sugars to 5-hydroxymethylfurfural (HMF), an important platform molecule for sustainable chemical production. First, screening experiments were carried out to identify a catalytic solvent system that achieves a balance between solvent stability, HMF yield, and cost-effectiveness. Our kinetic analysis on the identified system reveals that the fructose reactant undergoes a rate-determining dehydration step to form an unstable reactive intermediate. This intermediate further reacts competitively with other reactive species, such as the hexose reactants or the HMF product, ultimately lowering the HMF selectivity. The calculated relative activation energies of these reactions post rate-determining step provide intuitive insights into the effects of temperature, co-existing reactive species, as well as the previously unexplained effect of feed concentration on HMF selectivity. Additionally, we propose a novel reaction strategy that significantly enhances HMF yield when compared to a traditional batch synthesis. Notably, a high HMF yield of 74 % was achieved with an extreme 55 wt% fructose loading on an aqueous basis (20 wt% loading on a total weight basis) in a low-boiling 80 wt% dioxane/water mixture using an HCl catalyst at 393 K.

Cluster-Cluster Co-Nucleation Induced Defective Polyoxometalate-Based Metal-Organic Frameworks for Efficient Tandem Catalysis.

The construction of defective sites is one of the effective strategies to create high-activity Metal-Organic frameworks (MOFs) catalysts. However, traditional synthesis methods usually suffer from cumbersome synthesis steps and disordered defect structures. Herein, a cluster-cluster co-nucleation (CCCN) strategy is presented that involves the in situ introduction of size-matched functional polyoxometalates (H6P2W18O62, {P2W18}) to intervene the nucleation process of cluster-based MOFs (UiO-66), achieving one-step inducement of exposed defective sites without redundant post-processing. POM-induced UiO-66 ({P2W18}-0.1@UiO-66) exhibits a classical reo topology for well-defined cluster defects. Moreover, the defective sites and the interaction between POM and skeletal cluster nodes are directly observed by Integrated Differential Phase Contrast in Scanning Transmission Electron Microscopy (iDPC-STEM). Owing to the molecular-level proximity between defective sites and POM in the same nano-reaction space, {P2W18}-0.1@UiO-66 exhibits efficient tandem catalysis in the preparation of γ-valerolactone (γ-GVL) from laevulinic acid (LA) by the combination of Lewis and Brønsted acids with 11 times higher performance than defective UiO-66 formed by conventional coordination modulation strategy. The CCCN strategy is applicable to different POM and has the potential to be extended to other cluster-based MOFs, which will pave a new way for the construction of functional MOFs with multi-centered synergistic catalysis.

Synthesis of ZSM-5 Zeolite Nanosheets with Tunable Silanol Nest Contents across an Ultra-wide pH Range and Their Catalytic Validation.

Zeolite synthesis under acidic conditions has always presented a challenge. In this study, we successfully prepared series of ZSM-5 zeolite nanosheets (Z-5-SCA-X) over a broad pH range (4 to 13) without the need for additional supplements. This achievement was realized through aggregation crystallization of ZSM-5 zeolite subcrystal (Z-5-SC) with highly short-range ordering and ultrasmall size extracted from the synthetic system of ZSM-5 zeolite. Furthermore, the crystallization behavior of Z-5-SC was investigated, revealing its non-classical crystallization process under mildly alkaline and acidic conditions (pH<10), and the combination of classical and non-classical processes under strongly alkaline conditions (pH≥10). What's particularly intriguing is that, the silanol nest content in the resultant Z-5-SCA-X samples appears to be dependent on the pH values during the Z-5-SC crystallization process rather than its crystallinity. Finally, the results of the furfuryl alcohol etherification reaction demonstrate that reducing the concentration of silanol nests significantly enhances the catalytic performance of the Z-5-SCA-X zeolite. The ability to synthesize zeolite in neutral and acidic environments without the additional mineralizing agents not only broadens the current view of traditional zeolite synthesis but also provides a new approach to control the silanol nest content of zeolite catalysts.

Synthesis of ZSM‐5 Zeolite Nanosheets with Tunable Silanol Nest Contents across an Ultra‐wide pH Range and Their Catalytic Validation

AbstractZeolite synthesis under acidic conditions has always presented a challenge. In this study, we successfully prepared series of ZSM‐5 zeolite nanosheets (Z‐5‐SCA‐X) over a broad pH range (4 to 13) without the need for additional supplements. This achievement was realized through aggregation crystallization of ZSM‐5 zeolite subcrystal (Z‐5‐SC) with highly short‐range ordering and ultrasmall size extracted from the synthetic system of ZSM‐5 zeolite. Furthermore, the crystallization behavior of Z‐5‐SC was investigated, revealing its non‐classical crystallization process under mildly alkaline and acidic conditions (pH&lt;10), and the combination of classical and non‐classical processes under strongly alkaline conditions (pH≥10). What's particularly intriguing is that, the silanol nest content in the resultant Z‐5‐SCA‐X samples appears to be dependent on the pH values during the Z‐5‐SC crystallization process rather than its crystallinity. Finally, the results of the furfuryl alcohol etherification reaction demonstrate that reducing the concentration of silanol nests significantly enhances the catalytic performance of the Z‐5‐SCA‐X zeolite. The ability to synthesize zeolite in neutral and acidic environments without the additional mineralizing agents not only broadens the current view of traditional zeolite synthesis but also provides a new approach to control the silanol nest content of zeolite catalysts.

Sustainable Harnessing of Waste Polycarbonate for Synthesizing Activated Furans to Generate Stenhouse Adducts on Polymer Surface.

Plastics are versatile materials, offering lightweight, durable, and affordable solutions across various industries. However, their non-degradable nature poses challenges by end of their life. This study presented an innovative carbonyl extraction method to utilize waste poly(bisphenol A carbonate) (PC) as reaction precursor to synthesis of activated furan as precursor for photoswitchable Stenhouse adducts. This innovative chemical strategy not only generated N,N'-functionalized barbiturates but also provided an eco-friendly and cost-effective alternative to traditional synthesis methods. The method presented hereby not only promotes sustainability by repurposing waste polycarbonate as carbonyl equivalent under green conditions but also yielded reusable bisphenol A (BPA). Furthermore, the derived activated furans exhibited their functionality by forming colored donor-acceptor Stenhouse adducts (DASAs) on aminated polymer surfaces. This work demonstrated a transition from a linear plastics economy toward a circular one, highlighting the potential of plastic waste as a resource for creating materials with improved properties.

Cascade Sequence of Photooxygenation-Epoxidation for the Flow Synthesis of Epoxy Alcohols.

A photooxygenation-epoxidation cascade sequence converting alkenes to epoxy alcohols was developed and evaluated in batch and continuous-flow systems. In the batch system, the undesired interactions between the photooxygenation and epoxidation catalysts resulted in suboptimal yields, whereas the fine control of reaction parameters in the flow system allowed the allyl hydroperoxides produced through photooxygenation of alkenes to be rapidly converted to epoxy alcohols in yields of up to 93%. The developed procedure allows one to avoid an important synthetic bottleneck, works well where traditional batch synthesis fails, and can be scaled up to meet the needs of industrial production, thus presenting a valuable addition to the toolbox of practicing organic chemists.