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1.
Chem Commun (Camb) ; 58(53): 7419-7422, 2022 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-35695323

RESUMO

Here we report a photocatalytic system based on crystalline carbon nitrides (PHI) and highly dispersed transition metals (Fe, Co and Cu) for controlled methane photooxidation to methanol under mild conditions. The Cu-PHI catalyst showed a remarkable methanol production (2900 µmol g-1) in 4 hours, with a turnover number of 51 moles of oxygenated liquid product per mole of Cu. To date, this result is the highest value for methane oxidation under mild conditions (1 bar, 25 °C).

2.
Adv Mater ; 34(8): e2108493, 2022 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-34882864

RESUMO

Laser-induced forward transfer (LIFT) has the potential to be an alternative approach to atomic force microscopy based scanning probe lithography techniques, which have limitations in high-speed and large-scale patterning. However, traditional donor slides limit the resolution and chemical flexibility of LIFT. Here, a hematite nanolayer absorber for donor slides to achieve high-resolution transfers down to sub-femtoliters is proposed. Being wettable by both aqueous and organic solvents, this new donor significantly increases the chemical scope for the LIFT process. For parallel amino acid coupling reactions, the patterning resolution can now be increased more than five times (>111 000 spots cm- 2 for hematite donor vs 20 000 spots cm- 2 for standard polyimide donor) with even faster scanning (2 vs 6 ms per spot). Due to the increased chemical flexibility, other types of reactions inside ultrasmall polymer reactors: copper (I) catalyzed click chemistry and laser-driven oxidation of a tetrahydroisoquinoline derivative, suggesting the potential of LIFT for both deposition of chemicals, and laser-driven photochemical synthesis in femtoliters within milliseconds can be explored. Since the hematite shows no damage after typical laser transfer, donors can be regenerated by heat treatment. These findings will transform the LIFT process into an automatable, precise, and highly efficient technology for high-throughput femtoliter chemistry.

3.
Angew Chem Int Ed Engl ; 61(6): e202112204, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-34860450

RESUMO

The role of intermediate phases in CeO2 mesocrystal formation from aqueous CeIII solutions subjected to γ-radiation was studied. Radiolytically formed hydroxyl radicals convert soluble CeIII into less soluble CeIV . Transmission electron microscopy (TEM) and X-ray diffraction studies of samples from different stages of the process allowed the identification of several stages in CeO2 mesocrystal evolution following the oxidation to CeIV : (1) formation of hydrated CeIV hydroxides, serving as intermediates in the liquid-to-solid phase transformation; (2) CeO2 primary particle growth inside the intermediate phase; (3) alignment of the primary particles into "pre-mesocrystals" and subsequently to mesocrystals, guided by confinement of the amorphous intermediate phase and accompanied by the formation of "mineral bridges". Further alignment of the obtained mesocrystals into supracrystals occurs upon slow drying, making it possible to form complex hierarchical architectures.

4.
J Am Chem Soc ; 143(25): 9377-9384, 2021 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-34128662

RESUMO

Ionic liquids are well known for their high gas absorption capacity. It is shown that this is not a solvent constant, but can be enhanced by another factor of 10 by pore confinement, here of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate (EmimOAc) in the pores of carbon materials. A matrix of four different carbon compounds with micro- and mesopores as well as with and without nitrogen doping is utilized to investigate the influence of the carbons structure on the nitrogen uptake in the pore-confined EmimOAc. In general, the absorption is most improved for IL in micropores and in nitrogen-doped carbon. This effect is so large that it is already seen in TGA and DSC experiments. Due to the low vapor pressure of the IL, standard volumetric sorption experiments can be used to quantify details of this effect. It is reasoned that it is the change of the molecular arrangement of the ions in the restricted space of the pores that creates additional free volume to host molecular nitrogen.

5.
J Phys Chem B ; 124(23): 4843-4850, 2020 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-32423211

RESUMO

Polymer-grafted nanoparticles stabilized in ionic liquid (IL)-solvent mixtures are investigated by using transmission electron microscopy, dynamic light scattering, and electrochemical impedance spectroscopy. The ionic conductivity of IL-solvent mixtures with the polymer-grafted nanoparticles is found to be higher than that of nanoparticles in the IL. These particles offer additional interactions between polymer and IL, which can mitigate solvation in ILs with solvents. Motivated by this, we present the conductivity data of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) with poly(methyl methacrylate) (PMMA)-grafted particles in good and bad solvents and further discuss how graft density influences the swelling of PMMA and solvation characteristics of HMIM-TFSI. We found that HMIM-TFSI-acetonitrile containing high grafting density particles has a higher conductivity than that of the HMIM-TFSI-methanol mixture with grafted particles. Thus, solubility of PMMA in acetonitrile and preferential interactions between PMMA-HMIM-TFSI are shown to govern the swelling, solvation, and conductive properties of IL with the polymer-grafted nanoparticles.

6.
Angew Chem Int Ed Engl ; 59(35): 15061-15068, 2020 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-32412175

RESUMO

Polymeric carbon nitride materials have been used in numerous light-to-energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K-PHI)-a benchmark carbon nitride material in photocatalysis-by means of X-ray powder diffraction and transmission electron microscopy. Using the crystal structure of K-PHI, periodic DFT calculations were performed to calculate the density-of-states (DOS) and localize intra band states (IBS). IBS were found to be responsible for the enhanced K-PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, in addition to the direct recombination, can also undergo singlet-triplet intersystem crossing. We utilized the K-PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (1 O2 ) as a starting point to synthesis up to 25 different N-rich heterocycles.

7.
Sci Rep ; 10(1): 5832, 2020 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-32242048

RESUMO

The potassium salt of polyheptazine imide (K-PHI) is a promising photocatalyst for various chemical reactions. From powder X-ray diffraction data an idealized structural model of K-PHI has been derived. Using atomic coordinates of this model we defined an energetically optimized K-PHI structure, in which the K ions are present in the pore and between the PHI-planes. The distance between the anion framework and K+ resembles a frustrated Lewis pair-like structure, which we denote as frustrated Coulomb pair that results in an interesting adsorption environment for otherwise non-adsorbing, non-polar gas molecules. We demonstrate that even helium (He) gas molecules, which are known to have the lowest boiling point and the lowest intermolecular interactions, can be adsorbed in this polarized environment with an adsorption energy of  - 4.6 kJ mol-1 per He atom. The interaction between He atoms and K-PHI is partially originating from charge transfer, as disclosed by our energy decomposition analysis based on absolutely localized molecular orbitals. Due to very small charge transfer interactions, He gas adsorption saturates at 8 at%, which however can be subject to further improvement by cation variation.

8.
Adv Mater ; 32(9): e1903942, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31984551

RESUMO

Poly(heptazine imides) hosting cobalt ions as countercations are presented as promising electrocatalysts for the oxygen evolution reaction (OER). A facile mixed-salt melt-assisted condensation is developed to prepare such cobalt poly(heptazine imides) (PHI-Co). The Co ions can be introduced in well-controlled amounts using this method, and are shown to be atomically dispersed within the imide-linked heptazine matrix. When applied to electrocatalytic OER, PHI-Co shows a remarkable activity with an overpotential of 324 mV and Tafel slope of 44 mV dec-1 in 1 m KOH.

9.
Angew Chem Int Ed Engl ; 58(52): 18813-18816, 2019 12 19.
Artigo em Inglês | MEDLINE | ID: mdl-31621138

RESUMO

Artificial humic acids (A-HA) made from biomass in a hydrothermal process turn otherwise highly insoluble phosphates (e.g. iron phosphate as a model) into highly available phosphorus, which contributes to the fertility of soils and the coupled plant growth. A detailed electron microscopy study revealed etching of the primary iron phosphate crystals by the -COOH and phenolic groups of humic acids, but also illustrated the importance of the redox properties of humic matter on the nanoscale. The combined effects result in the formation of then bioavailable phosphate nanoparticles stabilized by humic matter. Typical agricultural chemical tests indicate that the content of total P and directly plant-available P improved largely. Comparative pot planting experiments before and after treatment of phosphates with A-HA demonstrate significantly enhanced plant growth, as quantified in higher aboveground and belowground plant biomass.


Assuntos
Fertilizantes/análise , Substâncias Húmicas/análise , Fosfatos/química , Solo/química
10.
Nanoscale ; 11(42): 19832-19841, 2019 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-31368472

RESUMO

We incorporated polymer-grafted nanoparticles into ionic and zwitterionic liquids to explore the solvation and confinement effects on their heterogeneous dynamics using quasi-elastic neutron scattering (QENS). 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) mixed with deuterated poly(methyl methacrylate) (d-PMMA)-grafted nanoparticles is studied to unravel how dynamic coupling between PMMA and HMIM-TFSI influence the fast and slow diffusion characteristics of the HMIM+ cations. The zwitterionic liquid, 1-butyl-3-methyl imidazole-2-ylidene borane (BMIM-BH3) is critically selected and mixed with PMMA-grafted nanoparticles for comparison in this work as its ions do not self-dissociate and it does not couple with PMMA through ion-dipole interactions as HMIM-TFSI does. We find that long-range unrestricted diffusion of HMIM+ cations is higher in well-dispersed particles than in aggregated particle systems, whereas the localized diffusion of HMIM+ is measured to be higher in close-packed particles. Translational diffusion dynamics of BMIM-BH3 is not influenced by any particle structures suggesting that zwitterions do not interact with PMMA. This difference between two ionic liquid types enables us to decouple polymer effects from the diffusion of ionic liquids, which is integral to understand the ionic transport mechanism in ionic liquids confined in polymer-grafted nanoparticle electrolytes.

11.
J Phys Chem Lett ; 10(18): 5514-5518, 2019 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-31408354

RESUMO

Control over particle size, size distribution, and colloidal stability are central aims in producing functional nanomaterials. Recently, biomimetic approaches have been successfully used to enhance control over properties in the synthesis of those materials. Magnetotactic bacteria produce protein-stabilized magnetite away from its thermodynamic equilibrium structure. Mimicking the bacteria's proteins using poly-l-arginine we show that by simply increasing the pH, the dimensions of magnetite increase and a single- to mesocrystal transformation is induced. Using synchrotron X-ray diffraction and transmission electron microscopy, we show that magnetite nanoparticles with narrow size distributions and average diameters of 10 ± 2 nm for pH 9, 20 ± 2 nm for pH 10, and up to 40 ± 4 nm for pH 11 can be synthesized. We thus selectively produce superparamagnetic and stable single-domain particles merely by controlling the pH. Remarkably, while an increase in pH brings about a thermodynamically driven decrease in size for magnetite without additives, this dependency on pH is inverted when poly-l-arginine is present.

12.
Small ; 15(37): e1901986, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31264774

RESUMO

Synthesis of 3D flower-like zinc-nitrilotriacetic acid (ZnNTA) mesocrystals and their conformal transformation to hierarchically porous N-doped carbon superstructures is reported. During the solvothermal reaction, 2D nanosheet primary building blocks undergo oriented attachment and mesoscale assembly forming stacked layers. The secondary nucleation and growth preferentially occurs at the edges and defects of the layers, leading to formation of 3D flower-like mesocrystals comprised of interconnected 2D micropetals. By simply varying the pyrolysis temperature (550-1000 °C) and the removal method of in the situ-generated Zn species, nonporous parent mesocrystals are transformed to hierarchically porous carbon flowers with controllable surface area (970-1605 m2 g-1 ), nitrogen content (3.4-14.1 at%), pore volume (0.95-2.19 cm3 g-1 ), as well as pore diameter and structures. The carbon flowers prepared at 550 °C show high CO2 /N2 selectivity due to the high nitrogen content and the large fraction of (ultra)micropores, which can greatly increase the CO2 affinity. The results show that the physicochemical properties of carbons are highly dependent on the thermal transformation and associated pore formation process, rather than directly inherited from parent precursors. The present strategy demonstrates metal-organic mesocrystals as a facile and versatile means toward 3D hierarchical carbon superstructures that are attractive for a number of potential applications.

13.
ChemSusChem ; 12(12): 2628-2636, 2019 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-30994965

RESUMO

The need for more sustainable products and processes has led to the use of new methodologies with low carbon footprints. In this work, an efficient tandem process is demonstrated for the liquid-phase catalytic upgrading of lignocellulosic biomass-derived γ-valerolactone (GVL) with trioxane (Tx) to α-methylene-γ-valerolactone (MeGVL) in flow system using Cs-loaded hierarchical beta zeolites. The introduction of mesopores along with the presence of basic sites of mild strength leads to MeGVL productivity 20 times higher than with the bulk beta zeolite, reaching 0.325 mmol min-1 gcat -1 for the best-performing catalyst, the highest value reported so far. This catalyst proves stable upon reuse in consecutive cycles, which is ascribed to the partial depletion of the basic sites. The obtained MeGVL is subjected to visible-light-induced polymerization, resulting in a final material with similar properties to the widely used poly(methyl) methacrylate.

14.
Sci Rep ; 8(1): 16301, 2018 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-30390023

RESUMO

Carbon nanodots (CNDs) doped with Tb ions were synthesized using different synthetic routes: hydrothermal treatment of a solution containing carbon source (sodium dextran sulfate) and TbCl3; mixing of CNDs and TbCl3 solutions; freezing-induced loading of Tb and carbon-containing source into pores of CaCO3 microparticles followed by hydrothermal treatment. Binding of Tb ions to CNDs (Tb-CND coupling) was confirmed using size-exclusion chromatography and manifested itself through a decrease of the Tb photoluminescence lifetime signal. The shortest Tb photoluminescence lifetime was observed for samples obtained by hydrothermal synthesis of CaCO3 microparticles where Tb and carbon source were loaded into pores via the freezing-induced process. The same system displays an increase of Tb photoluminescence via energy transfer with excitation at 320-340 nm. Based on the obtained results, freezing-induced loading of cations into CNDs using porous CaCO3 microparticles as reactors is proposed to be a versatile route for the introduction of active components into CNDs. The obtained CNDs with long-lived emission may be used for time-resolved imaging and visualization in living biological samples where time-resolved and long-lived luminescence microscopy is required.

15.
Dalton Trans ; 47(39): 14041-14051, 2018 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-30232497

RESUMO

The apatite-like NaLa9(GeO4)6O2:Nd3+,Ho3+ phosphor is prepared using the solid-state method. Rietveld refinement of high-resolution time-of-flight neutron powder diffraction measurements indicate that this compound crystallizes in the hexagonal system with space group P63/m, Z = 1 and unit cell parameters a = 9.88903(6) Å, c = 7.25602(5) Å, V = 614.521(7) Å3 at room temperature. The 4f sites are statistically occupied by La, Nd and Na, while 6h sites are occupied by La and Nd. Luminescence in the near- and middle-IR range caused by the transitions in neodymium and holmium ions is excited under 808 nm laser diode radiation. The highest emission intensity in NaLa9-x-yNdxHoy(GeO4)6O2 is attained at trace amounts of holmium, and it decreases sharply when y increases to 0.01. The IR phosphors have a good thermal stability and exhibit a very weak upconversion emission in the red spectral range upon 808 nm excitation. A scheme of excitation and emission pathways involving ground/excited state absorption, energy transfer, cross-relaxation, nonradiative multiphonon relaxation processes in Nd3+ and Ho3+ ions has been proposed. The data analysis indicates that Nd3+ ions serve as sensitizers for Ho3+ ions in these compounds, stimulating intense 2.1 µm and 2.7 µm emissions. These apatite-related germanate phosphors are promising materials for near- and middle-infrared solid-state lighting applications.

16.
Nat Commun ; 9(1): 2145, 2018 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-29858566

RESUMO

A major goal in materials science is to develop bioinspired functional materials based on the precise control of molecular building blocks across length scales. Here we report a protein-mediated mineralization process that takes advantage of disorder-order interplay using elastin-like recombinamers to program organic-inorganic interactions into hierarchically ordered mineralized structures. The materials comprise elongated apatite nanocrystals that are aligned and organized into microscopic prisms, which grow together into spherulite-like structures hundreds of micrometers in diameter that come together to fill macroscopic areas. The structures can be grown over large uneven surfaces and native tissues as acid-resistant membranes or coatings with tuneable hierarchy, stiffness, and hardness. Our study represents a potential strategy for complex materials design that may open opportunities for hard tissue repair and provide insights into the role of molecular disorder in human physiology and pathology.


Assuntos
Calcificação Fisiológica , Dentina/metabolismo , Elastina/metabolismo , Proteínas Intrinsicamente Desordenadas/metabolismo , Minerais/metabolismo , Sequência de Aminoácidos , Esmalte Dentário/química , Dentina/química , Dentina/ultraestrutura , Elastina/química , Elastina/ultraestrutura , Humanos , Hidroxiapatitas/química , Hidroxiapatitas/metabolismo , Proteínas Intrinsicamente Desordenadas/química , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Minerais/química , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios X
17.
Sci Rep ; 8(1): 9394, 2018 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-29925932

RESUMO

Synthesis of carbon nanodots (CNDs) in confined geometry via incorporation of dextran sulphate into pores of CaCO3 microparticles is demonstrated. The preparation process included three steps: co-precipitation of solutions of inorganic salts and carbon source, thermal treatment and CaCO3 matrix removal. We show that geometric constraints can be used to precisely control the amount of source material and to avoid formation of large carbon particles. Analysis of TEM data shows particle size of ~3.7 nm with narrow size distribution. Furthermore, we found that variation in pore morphology has a clear effect on CNDs structure and optical properties. CNDs with graphene oxide like structure were obtained in the nanoporous outer shell layer of CaCO3 microparticles, while less ordered CNDs with the evidence of complex disordered carbons were extracted from the inner microcavity. These results suggest that confined volume synthesis route in CaCO3 nanopores can be used to precisely control the structure and optical properties of CNDs.

18.
ACS Biomater Sci Eng ; 4(7): 2453-2462, 2018 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-33435109

RESUMO

Cerium oxide nanoparticles (nanoceria) are regarded as one of the most promising inorganic antioxidants for biomedical applications. Considering nanoceria as a potential therapeutic agent, we aimed to develop a robust system for its intracellular delivery using layer-by-layer polyelectrolyte microcapsules. We have shown that citrate-stabilized cerium oxide nanoparticles can be effectively incorporated into the structure of polyelectrolyte microcapsules made from biodegradable and nonbiodegradable polymers. The structure and morphology of synthesized microcapsules were investigated and analyzed using confocal laser scanning microscopy, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and UV/vis spectroscopy. Results of experiments in vitro on B50 neuroblastoma cells confirmed nanoceria delivery into the cell while maintaining their antioxidant properties. The results presented confirm polyelectrolyte microcapsules to be an efficient intracellular delivery system for therapeutic nanoparticles.

19.
Sci Rep ; 7(1): 6639, 2017 07 26.
Artigo em Inglês | MEDLINE | ID: mdl-28747706

RESUMO

Realising engineering ceramics to serve as substrate materials in high-performance terahertz(THz) that are low-cost, have low dielectric loss and near-dispersionless broadband, high permittivity, is exceedingly demanding. Such substrates are deployed in, for example, integrated circuits for synthesizing and converting nonplanar and 3D structures into planar forms. The Rutile form of titanium dioxide (TiO2) has been widely accepted as commercially economical candidate substrate that meets demands for both low-loss and high permittivities at sub-THz bands. However, the relationship between its mechanisms of dielectric response to the microstructure have never been systematically investigated in order to engineer ultra-low dielectric-loss and high value, dispersionless permittivities. Here we show TiO2 THz dielectrics with high permittivity (ca. 102.30) and ultra-low loss (ca. 0.0042). These were prepared by insight gleaned from a broad use of materials characterisation methods to successfully engineer porosities, second phase, crystallography shear-planes and oxygen vacancies during sintering. The dielectric loss achieved here is not only with negligible dispersion over 0.2-0.8 THz, but also has the lowest value measured for known high-permittivity dielectrics. We expect the insight afforded by this study will underpin the development of subwavelength-scale, planar integrated circuits, compact high Q-resonators and broadband, slow-light devices in the THz band.

20.
Dalton Trans ; 46(30): 9995-10002, 2017 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-28726886

RESUMO

A facile synthesis of 3d-metal based electro-catalysts directly incorporated into a carbon support was carried out by γ-radiation. Transition metals of period 4, i.e. Ni and Co, were precipitated and reduced from their respective salt solutions. The obtained materials were characterized by XRD, SEM, SQUID and the BET methods. Thereafter, the electrodes for fuel cells were fabricated out of synthesized material and their electrochemical performance for the oxygen reduction reaction in 6 M KOH was measured. Although the concentrations of Co and Ni in the electrode material were low (3.4% Co and 0.4% Ni) after reduction by irradiation, both the Ni and Co-based gas diffusion electrodes showed high catalytic activity for oxygen reduction both at room temperature and at 60 °C.

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