Direct Synthesis Research Articles

Direct Synthesis of Metasurfaces for Efficient Space- to Surface-Wave Conversion and Beamforming

Direct Synthesis of Metasurfaces for Efficient Space- to Surface-Wave Conversion and Beamforming

Direct synthesis of low-silica ZSM-48 zeolite via seed-assisted hydrothermal synthesis with 1,6-hexanediamine as template

ZSM-48 zeolite is characteristic of 10-member ring (10-MR) one-dimensional tubular channel structure and finds extensive applications in catalytic hydroisomerization reactions. Here we developed an efficient synthetic strategy for low-silica ZSM-48 zeolite with a SiO2/Al2O3 ratio at 30∼176 via a seed-assisted hydrothermal synthesis method, overcoming the limit that 1,6-hexanediamine (HDA) template can only be used to synthesize high-silica (i.e., SiO2/Al2O3 ratio >200) zeolites. A two-step crystallization procedure coupled with zeolite seed-assisted synthesis strategy was enrolled to realize well crystallized ZSM-48 zeolites, in which the zeolite nuclei are sufficiently produced at the nucleation temperature at 100 °C for 24 h with the aid of zeolite seeds, and the zeolite growth is proceeded at the crystallization temperature at 160 °C for 48 h. The morphology and particle size of low-silica ZSM-48 have been manipulated by adjusting the synthetic parameters, such as the alkalinity and silicon source of aluminosilicate gel for zeolite, the crystallization manner (static or dynamic crystallization), as well as the presence of additive (i.e., sodium chloride). The as-synthesized ZSM-48 zeolite exhibits a significantly high acid content of 0.194 mmol/g, highlighting its potential as an excellent acidic support for hydroisomerization catalysts. The cost-effective and environmentally friendly synthesis strategy, which is anticipated to expand the application of alkylamine organic templates in the synthesis of low-silica ZSM-48 zeolite.

Bimetallic MnZn-MOF-74 with enhanced percentage of MnIII: Efficiently catalytic activity for direct oxidative carboxylation of olefins to cyclic carbonates under mild and solvent-free condition

Multi-functional MOF catalyst with oxidative- and acid- centers showed potential in olefins oxidative carboxylation to cyclic carbonates directly. In this work, a series of bimetallic MnZn-MOF-74 with different molar ratios of Mn and Zn were synthesized successfully through a one-pot facile method. Thoroughly characterization indicated that the existence of Zn regulated the valance state distribution of Mn in the obtained MnZn-MOF-74. Mn99.3Zn0.7-MOF-74 with the highest ratio of MnIII (61.3 %) performed the most efficient activity for olefin direct tandem oxidative carboxylation reaction using aqueous tert-butyl hydroperoxide oxidant under solvent-free condition of 90 °C, 1.0 MPa CO2 and 4 h. Mn99.3Zn0.7-MOF-74 also showed satisfactory versatility and recyclability. Based on the experiments, a feasible mechanism was presented. Thanks to the high ratio of active MnIII as main oxidative center, the coordination unsaturated bimetal Mn and Zn as Lewis-acid sites, O2– of metal − O as Lewis-base sites and combined effect with Bu4NBr cocatalyst, Mn99.3Zn0.7-MOF-74 presented efficient performance for the direct synthesis of cyclic carbonates from olefins. The metal Zn in MOF can regulate the valance state distribution of Mn and result in efficient catalytic property, presenting a potential avenue for direct oxidative carboxylation reaction of olefins to cyclic carbonates synthesis.

Next-generation photodynamic antimicrobial materials made by direct synthesis of functional bacterial cellulose.

Bacterial cellulose (BC) regularly uses chemical or physical modifications to produce antimicrobial wound dressings. However, there is a risk of loss of functional components during application. Moreover, a significant hurdle lies in successfully integrating durable and highly effective bactericidal entities with BC. Herein, we successfully synthesized a photodynamic antibacterial cellulose through direct in situ microbial fermentation, incorporating the photosensitizer protoporphyrin IX-modified glucosamine (PPIX-GlcN) into cellulose to form PIXX-BC biopolymers. Excitingly, the PPIX-BC membrane exhibited robust and uniform red fluorescence, which is crucial for monitoring the bacterial fermentation process. Our results demonstrated that the biocompatibility PPIX-BC membrane possessed potent light-triggered photodynamic bactericidal activity, effectively suppressing the growth of E. coli and S. aureus while also promoting skin wounds repair. Consequently, this research validated the possibility of leveraging microorganisms to bio-functionalize BC, conferring it with photocatalytic antibacterial properties. Furthermore, successfully modification of the microorganisms' glucose carbon source offers valuable insights into biosynthesis of other living materials through microbial metabolism.

Core-shell structured composite high-efficiency catalyst Co@Pd/TiO2 with a compressed-strain Pd shell for the direct synthesis of H2O2

Direct synthesis of H2O2 from H2 and O2 still faces the dilemma of low selectivity and productivity due to the O-O bond dissociation. To expedite the resolution of this issue, we introduce a core–shell structured catalyst Co@Pd/TiO2 with a compressed-strain Pd shell. The Co@Pd/TiO2 catalyst demonstrates a superior H2O2 productivity of 6.95 × 103 mmol·gPd-1·h−1 and H2O2 selectivity of 98.1 %, with enhancements of over 192 % and 139 %, respectively, when compared to Pd/TiO2. The construction of the compressed-strain Pd shell on the Co@Pd/TiO2 catalyst induces a winder width (wd) and a lower center (εd) of the Pd d-band, allowing the Co@Pd/TiO2 catalyst to achieve the following benefits for improving H2O2 selectivity and productivity: (1) Reducing the degree of electron back-donation to O2* (* denotes adsorbed state, the same below), thus inhibiting the cleavage of the O-O bond in O2*; (2) Showing a weaker Pd-O bond strength, which stabilizes the OOH* species and suppresses the breakage of the O-O bond therein; (3) Weakening the interaction between the catalyst and chemical substances, thereby restraining H2O2 degradation.

Direct Synthesis of Ti-Al Compound Powders by Electrolysis in Molten LiCl-KCl

The deposition potential difference between Ti and Al is only 70 mV. The deposition reaction of Ti-Al compound happens at the potentials slightly higher than that of metallic Ti and Al. Through galvanostatic electrolysis of mixture solution of Al and Ti ions, all kinds of titanium aluminides can be directly synthesized. The composition of the product compound can be selected through adjusting the combination of Ti and Al ions in the electrolyte.

Direct synthesis of Cu-TiO<sub>2</sub>-SBA-16 photocatalysts and its application for the oxidative desulfurization of fuel oil model

In this study, the Cu-TiO2-SBA-16 photocatalytic materials were successfully prepared by direct hydrothermal synthesis method. The products were characterized by X-ray diffraction (XRD), Ultraviolet–Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), energy dispersive X-ray (EDX), transmission electron microscopy (TEM), N2 adsorption–desorption isotherms, X-ray photoelectron spectroscopy (XPS) methods. The analysis illustrated that Cu-TiO2 nanocrystals were successfully incorporated into the SBA-16 mesopores. The photocatalytic activity of these Cu-TiO2-SBA-16 mesoporous materials have been tested by the oxidative desulfurization reaction of dibenzothiophene (DBT) using H2O2 as an oxidant under UV light irradiation. The results showed that the Cu-TiO2-SBA-16 mesoporous materials prepared at the Cu/Ti mole ratios of 0.05 showed higher photocatalytic activity than the rest due to the decrease in band gap energy.

Chemical Vapor Deposited Thin Palladium Sulfide Crystals for Highly Photoresponsive Photodetector

AbstractNonlayered palladium sulfide (PdS) is of interest due to its rich physical properties and promising applications in optoelectronic devices. However, the growth of thin nonlayered PdS remains challenging because of its intrinsic 3D lattice structure. Here, the first demonstration of the direct synthesis of thin rectangular PdS ribbons/flakes on SiO2/Si substrates by a facile chemical vapor deposition (CVD) approach is presented. The atomic structure and high crystalline quality of CVD‐derived PdS crystals are shown by scanning transmission electron microscopy. The nonlinear saturable absorption and absorption enhancement are revealed by using ultrafast optical pump‐probe spectroscopy, and the photocarrier dynamics present the hot phonon bottleneck and Auger recombination effects. Additionally, the Raman vibration modes display the polarization‐dependent properties verified by angle‐resolved polarized Raman spectroscopy. Importantly, the photodetector based on PdS ribbon demonstrates a decent photoresponsivity of ≈7.7 × 103 A W−1. This results provide an effective way to form thin nonlayered PdS with potential applications in the field of photodetection.

Properties of palladium-phosphorus catalysts supported on HZSM-5 zeolite in the direct synthesis of hydrogen peroxide

The properties of Pd/HZSM-5 and Pd–nP/HZSM-5 catalysts in direct synthesis and side processes of decomposition and hydrogenation of H2O2 under mild conditions in ethanol and aqueous-ethanol medium in the presence of an acid inhibitor were studied. Using HR-TEM, XRD and ICP MS methods, it was shown that as a result of modification with phosphorus, X-ray amorphous highly dispersed systems are formed, which represent structurally disordered solid solutions of phosphorus in palladium. The main reasons for the promoting effect of phosphorus on the yield of H2O2 are considered. It has been established that, along with phosphorus and acid modifiers, the use of a zeolite support in the H-form favors the inhibition of the side process of H2O2 decomposition.

Optimized Design of Direct Digital Frequency Synthesizer Based on Hermite Interpolation

To address the issue of suboptimal spectral purity in Direct Digital Frequency Synthesis (DDFS) within resource-constrained environments, this paper proposes an optimized DDFS technique based on cubic Hermite interpolation. Initially, a DDFS hardware architecture is implemented on a Field-Programmable Gate Array (FPGA); subsequently, essential interpolation parameters are extracted by combining the derivative relations of sine and cosine functions with a dual-port Read-Only Memory (ROM) structure using the cubic Hermite interpolation method to reconstruct high-fidelity target waveforms. This approach effectively mitigates spurious issues caused by amplitude quantization during the DDFS digitalization process while reducing data node storage units. Moreover, this paper introduces single-quadrant ROM compression technology to further diminish the required storage space. Experimental results indicate that, compared to traditional DDFS methods, the optimization scheme proposed in this work achieves a ROM resource compression ratio of 1792:1 and a 14-bit output Spurious-Free Dynamic Range (SFDR) of −88.134 dBc, effectively enhancing amplitude quantization precision and significantly lowering spurious levels. This significantly improves amplitude quantization precision and reduces spurious levels. The proposed scheme demonstrates notable advantages in both spectral performance and resource utilization efficiency, making it highly suitable for resource-constrained embedded systems and high-performance applications such as radar and communication systems.

Catalyst-Free [4+1] Annulation of α-Imidoyl Sulfoxonium Ylides and Diazo Compounds Enabling the Modular Synthesis of 2-Indanones and 3(2H)-Furanones.

A novel substrate-regulated [4+1] annulation of α-imidoyl sulfoxonium ylides with diazoketones under catalyst-free conditions is described. The reaction proceeds through a coupling of sulfoxonium ylides and in situ-generated ketenes to form the key reactive zwitterionic intermediates, followed by selective formation of C-C or C-O bonds to achieve five-membered ring systems. The cascade reaction permits the direct synthesis of synthetically useful 2-indanones and 3(2H)-furanones, which expands the reaction pattern of sulfoxonium ylides in annulation transformation.

Unraveling the adsorption-limited hydrogen oxidation reaction at palladium surface via in situ electron microscopy

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H2O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remain elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied in situ, to investigate intermediate reaction stages via gas cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by precursors' adsorption. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions.

Direct asymmetric synthesis of β-branched aromatic α-amino acids using engineered phenylalanine ammonia lyases

β-Branched aromatic α-amino acids are valuable building blocks in natural products and pharmaceutically active compounds. However, their chemical or enzymatic synthesis is challenging due to the presence of two stereocenters. We design phenylalanine ammonia lyases (PAL) variants for the direct asymmetric synthesis of β-branched aromatic α-amino acids. Based on extensive computational analyses, we unravel the enigma behind PAL’s inability to accept β-methyl cinnamic acid (β-MeCA) as substrate and achieve the synthesis of the corresponding amino acids of β-MeCA and analogs using a double (PcPAL-L256V-I460V) and a triple mutant (PcPAL-F137V-L256V-I460V). The reactions are scaled-up using an optimized E. coli based whole-cell biotransformation system to produce ten β-branched phenylalanine analogs with high diastereoselectivity (dr > 20:1) and enantioselectivity (ee > 99.5%) in yields ranging from 41-71%. Moreover, we decipher the mechanism of PcPAL-L256V-I460V for the acceptance of β-MeCA and converting it with excellent stereoselectivity by computational simulations. Thus, this study offers an efficient method for synthesizing β-branched aromatic α-amino acids.

Enhanced Intramolecular Hole Transfer in Block Copolymer Enables >15% and Operational Stable Single-Material-Organic Solar Cells.

Recent studies on narrow bandgap all-conjugated block copolymer (BCP) single-material-organic solar cells (SMOSCs) have made unprecedented progress in power conversion efficiency (PCE); however, it still lacks understanding of the structure-property relationship in these highly mixed materials. Herein, the impact of different synthetic protocols (direct synthesis (d-BCP) versus sequential synthesis (s-BCP)) is first investigated on the relevant photovoltaic properties. Targeting the same BCP, namely PBDB-T-b-PYIT, it is found that the change in polymerization reaction leads to quite different optical and transport properties. The d-BCP outputs a record-high PCE of 15.02% for SMOSCs as well as enhanced operation stability under simulated 1-sun illumination, which is significantly higher than that of s-BCP (10.33%) and even close to its bulk heterojunction (BHJ) counterparts. Detailed transient absorption spectroscopy reveals ultrafast dynamics of charge transfer (CT) and exciton dissociation in BCP. In together with morphology characterization, it is revealed that the d-BCP has more phase pure composition, enhanced molecular ordering, and higher intramolecular CT efficiency relative to those of s-BCP. These findings gain insight into both the structure and carrier dynamic of BCP and demonstrate the possibility of achieving high-efficiency and stable SMOSCs.

Optimized Incorporation of Silver Nanoparticles onto Cotton Fabric Using k-Carrageenan Coatings for Enhanced Antimicrobial Properties.

The incorporation of bactericidal properties into textiles is a widely sought-after aspect, and silver nanoparticles (AgNPs) can be used for this. Here, we evaluate a strategy for incorporating AgNPs into a cotton fabric. For this purpose, a bactericidal textile coating based on a composite of AgNPs and kappa-carrageenan (k-CA) was proposed. The composite was obtained by heating the silver precursor (AgNO3) directly in k-CA solution for green synthesis and in situ AgNPs stabilization. Cotton substrates were added to the heated composite solution for surface impregnation and hydrogel film formation after cooling. Direct synthesis of AgNPs on a fabric was also tested. The results showed that the application of a coating based on k-CA/AgNPs composite can achieve more than twice the silver loading on the fabric surface compared to the textile subjected to direct AgNPs incorporation. Furthermore, silver release tests in water showed that higher Ag+ levels were reached for k-CA/AgNPs-coated cotton. Therefore, inoculation tests with the bacteria Staphylococcus aureus (SA) using the agar diffusion method showed that samples covered with the composite resulted in significantly larger inhibition halos. This indicated that the use of the composite as a coating for cotton fabric improved its bactericidal activity against SA.

Direct Synthesis of Dimethyl Carbonate from Methanol and CO2 over ZrO2 Catalysts Combined with a Dehydrating Agent and a Cocatalyst

Zirconia nanocrystals as catalysts for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide have received significant interest recently. In this paper, three zirconia-based catalysts presenting different monoclinic and tetragonal phase contents are prepared and characterized by X-ray diffraction (XRD), N2 adsorption–desorption, transmission electron microscopy (TEM), and temperature-programmed desorption of NH3 and CO2 (NH3-TPD and CO2-TPD). The catalytic performances of these solids are evaluated in terms of DMC production. This production is low when using the bare zirconias, but it is significantly increased in the presence of 1,1,1-trimethoxymethane (TMM) playing the role of a dehydrating agent, which shifts the thermodynamic equilibrium. Moreover, the production of DMC is further improved by adding a second solid catalyst (cocatalyst), the molecular sieve 13X, to accelerate the hydration of TMM. Hence, the molecular sieve 13X plays a dual role by trapping water molecules formed by the reaction of DMC synthesis and providing strong acidic sites catalyzing TMM hydrolysis. To the best of our knowledge, the combination of two solid catalysts in the reaction medium to accelerate the water elimination to obtain higher DMC production from CO2 and methanol has never been reported.

Photosynthetic biohybrid systems for solar fuels catalysis.

Photosynthetic reaction center (RC) proteins are finely tuned molecular systems optimized for solar energy conversion. RCs effectively capture and convert sunlight with near unity quantum efficiency utilizing light-induced directional electron transfer through a series of molecular cofactors embedded within the protein core to generate a long-lived charge separated state with a useable electrochemical potential. Of current interest are new strategies that couple RC chemistry to the direct synthesis of energy-rich compounds. This Feature Article highlights recent work from our lab on RC and RC-inspired hybrid systems that capture the Sun's energy and convert it to chemical energy in the form of H2, a carbon-neutral energy source derived from water. Biohybrids made from the Photosystem I (PSI) RC are among the best photocatalytic H2-producing protein hybrids to date. Targeted self-assembly strategies that couple abiotic catalysts to PSI translate to catalyst incorporation at intrinsic PSI sites within thylakoid membranes to achieve complete solar water-splitting systems. RC-inspired biohybrids interface synthetic photosensitizers and molecular catalysts with small proteins to create photocatalytic systems and enable the spectroscopic discernment of the structural features and electron transfer processes that underpin solar-driven proton reduction. In total, these studies showcase the incredible scientific opportunities photosynthetic biohybrid research provides for harnessing the optimal qualities of both artificial and natural photosynthetic systems and developing materials that capture, convert, and store solar energy as a fuel.

Novel N-Substituted Isatin-Oxoindolin-1H-Benzo[D] Imidazole Fumarate as a New Class of JNK3 Inhibitor: Design, Synthesis, Molecular Modeling and its Biological Activity

Background: A direct synthesis of functionalized dimethyl fumarate derivatives of 2-(2-((E)-(2-oxoindolin-3-ylidene)methyl)-1H-benzo[d]imidazol-1-yl) is achieved via one-pot reac-tion involving 2-methyl-1H-benzo[d]imidazole and appropriate isatin in the presence of DMAD. Methods: Conversely, this one-pot reaction furnished, upon conduction at 60 o C, the 2-(2-((E)-(2-oxoindolin-3-ylidene)methyl)-1H-benzo[d]imidazol-1-yl) products. The biological activities were evaluated against JNK3 kinase. We chose to dock the compounds into the JNK3 binding site in order to comprehend the molecular underpinnings of the observed bioactivities. Results: The structures of the synthesized compound adduct were evidenced from NMR and MS spectral data and further confirmed by single-crystal X-ray diffraction. The biological activities revealing that the introduction of an alkyl group at the 1-position of the isatin moiety produced JNK3 inhibitors with IC50 values in the low micromolar range. Conclusion: This study synthesized a unique compound using a three-component method. Com-pound 4d showed high antitumor activity (IC50 = 6.5 μM) against JNK3 inhibitors, while com-pounds 4c, 4d, and 4f exhibited high selectivity. The research highlights the effectiveness of the one-pot reaction in creating medically useful hybrid compounds, marking a significant advance in medicinal chemistry.

Platelet Ceria Catalysts from Solution Combustion and Effect of Iron Doping for Synthesis of Dimethyl Carbonate from CO2

Solution combustion (SC) remains among the most promising synthetic strategies for the production of crystalline nanopowders from an aqueous medium, due to its easiness, time and cost‐effectiveness, scalability and eco‐friendliness. In this work, this method was selected to obtain anisometric ceria‐based nanoparticles applied as catalysts for the direct synthesis of dimethyl carbonate. The catalytic performances were studied for the ceria and Fe‐doped ceria from SC (CeO2‐SC, Ce0.9Fe0.1O2‐SC) in comparison with the ceria nanorods (CeO2‐HT, Ce0.9Fe0.1O2‐HT) obtained by hydrothermal (HT) method, one of the most studied systems in the literature. Indeed, the ceria nanoparticles obtained by SC were found to be highly crystalline, platelet‐shaped, arranged in a mosaic‐like assembly and with smaller crystallite size (≈6 nm vs. ≈17 nm) and higher surface area (80 m2 g‐1vs. 26 m2 g‐1) for the undoped sample with respect to the Fe‐doped counterpart. Although all samples exhibit an anisometric morphology that should favor the exposition of specific crystalline planes, HT‐samples showed better performances due to higher oxygen vacancies concentration and lower amount of strong basic and acid sites.

Direct Precursor Route for the Fabrication of LLZO Composite Cathodes for Solid-State Batteries.

Solid-state batteries based on Li7La3Zr2O12 (LLZO) garnet electrolyte are a robust and safe alternative to conventional lithium-ion batteries. However, the large-scale implementation of ceramic composite cathodes is still challenging due to a complex multistep manufacturing process. A new one-step route for the direct synthesis of LLZO during the manufacturing of LLZO/LiCoO2 (LCO) composite cathodes based on cheap precursors and utilizing the industrially established tape casting process is presented. It is shown that Al, Ta:LLZO can be formed directly in the presence of LCO from metal oxide precursors (LiOH, La2O3, ZrO2, Al2O3, and Ta2O5) by heating to 1050°C, eliminating the time- and energy-consuming synthesis of preformed LLZO powders. In addition, performance-optimized gradient microstructures can be produced by sequential casting of slurries with different compositions, resulting in dense and flat phase-pure cathodes without unwanted ion interdiffusion or secondary phase formation. Freestanding cathodes with a thickness of 85µm, a relative density of 95%, and an industrial relevant LCO loading of 15mg show an initial capacity of 82 mAh g-1 (63% of the theoretical capacity of LCO) in a solid-state cell with Li metal anodes, which is comparable to conventional LCO/LLZO cathodes and can be further improved in the future.