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1.
Artigo em Inglês | MEDLINE | ID: mdl-32412175

RESUMO

Polymeric carbon nitride materials have been successfully 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 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, beside 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 (1O2) as a starting point to synthesis up to 25 different N-rich heterocycles.

2.
J Colloid Interface Sci ; 575: 88-95, 2020 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-32361049

RESUMO

Complex aqueous emulsions represent a promising material platform for the encapsulation of cells, pharmaceuticals, or nutrients, for the fabrication of structured particles, as well as for mimicking the barrier-free compartmentalization of biomolecules found in living cells. Herein, we report a novel, simple, and scalable method of creating multicomponent aqueous droplets with highly uniform internal droplet morphologies that can be controllably altered after emulsification by making use of a thermal phase separation approach. Specifically, temperature-induced phase separation inside as-formed emulsion droplets comprising aqueous mixtures of two or more hydrophilic polymers allows for the generation of Janus and Cerberus emulsion droplets with adjustable internal morphologies that are solely controlled by a balance of interfacial tensions. We demonstrate our approach by applying both, microfluidic and scalable batch production, and present a detailed model study with predictive capabilities that enables fine-tuning and dynamically altering the droplet morphology as a function of types, molecular weights, and hydrophilicities of the polymers as well as the surfactant hydrophilic-lipophilic balance. The ability to rationally design complex aqueous emulsion droplets with previously unattainable dynamic control over their morphologies after emulsification entails the potential to design new responsive soft materials with implications for a variety of applications beyond encapsulation, including the design of complex adaptive and self-regulating materials, e.g. for chemical and biological sensing applications.

3.
Artigo em Inglês | MEDLINE | ID: mdl-32155311

RESUMO

Efficient and low-cost anode materials for the sodium-ion battery are highly desired to enable more economic energy storage. Effects on an ultrathin carbon nitride film deposited on a copper metal electrode are presented. The combination of effects show an unusually high capacity to store sodium metal. The g-C3 N4 film is as thin as 10 nm and can be fabricated by an efficient, facile, and general chemical-vapor deposition method. A high reversible capacity of formally up to 51 Ah g-1 indicates that the Na is not only stored in the carbon nitride as such, but that carbon nitride activates also the metal for reversible Na-deposition, while forming at the same time an solid electrolyte interface layer avoiding direct contact of the metallic phase with the liquid electrolyte.

4.
Nat Commun ; 11(1): 1387, 2020 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-32170119

RESUMO

Small organic radicals are ubiquitous intermediates in photocatalysis and are used in organic synthesis to install functional groups and to tune electronic properties and pharmacokinetic parameters of the final molecule. Development of new methods to generate small organic radicals with added functionality can further extend the utility of photocatalysis for synthetic needs. Herein, we present a method to generate dichloromethyl radicals from chloroform using a heterogeneous potassium poly(heptazine imide) (K-PHI) photocatalyst under visible light irradiation for C1-extension of the enone backbone. The method is applied on 15 enones, with γ,γ-dichloroketones yields of 18-89%. Due to negative zeta-potential (-40 mV) and small particle size (100 nm) K-PHI suspension is used in quasi-homogeneous flow-photoreactor increasing the productivity by 19 times compared to the batch approach. The resulting γ,γ-dichloroketones, are used as bifunctional building blocks to access value-added organic compounds such as substituted furans and pyrroles.

5.
Adv Mater ; : e1907702, 2020 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-32129563

RESUMO

A novel covalent, metal-free, photocatalytic material is prepared by thermal polymerization of barbituric acid (BA). The structure of the photocatalyst is analyzed by using scanning electron microscopy, X-ray diffraction, and infrared, UV-visible, and 1 H solution and 13 C solid-state NMR spectroscopy. The photodegradation efficiency of BA thermally polymerized at different temperatures is tested by photocatalytic degradation of aquatic rhodamine B (RhB) dye under visible-light irradiation. It is shown that heating BA at an optimized temperature of 300 °C, that is, still in the range that polymer-like polycondensation takes place, results in a photocatalyst that can remove RhB with 96% photodegradation efficiency after 70 min exposure to visible light. The polycondensation reaction of BA is identified to process through precipitation of trimer units as primary building blocks. Reference experiments such as addition of scavengers and saturation with oxygen are studied to understand the photodegradation process. It is shown that the presence of triethanolamine, and excess of oxygen and p-benzoquinone in the solution of RhB and photocatalyst (BA300) is not beneficial, but decreases the photodegradation efficiency.

6.
Artigo em Inglês | MEDLINE | ID: mdl-32091193

RESUMO

Porous carbon/nitrogen frameworks are an emerging class of noble organic materials with a wide range of potential applications. However, the design and controlled synthesis of those materials are still a challenge. Herein, we present the rational design of such a system with high microporosity, specific surface areas of up to 946 m2 g-1, and excellent condensation yields. The obtained noble frameworks were used for the delivery of larger organic molecules and changed the melting behavior of some daily drug molecules along their highly polarizable surfaces.

7.
ACS Nano ; 2020 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-31986009

RESUMO

Metal clusters, an emerging category of materials with molecular metal dispersity, have been proposed for versatile applications. In this work, we show an unexpected function of metal clusters, which can contribute to preparing 2D/2D superlattice-like heterostructures. The key step is to use metal clusters to adjust the surface charge of 2D nanosheets and, consequently, match the charge negativities per surface area for different 2D nanosheets, which facilitate the electrical-driven assembly of these nanosheets into a superlattice-like heterostructure in aqueous solutions. Accordingly, iron-cluster-directed cationic Fe-N-C nanosheets (Zeta potential: +30.4 mV) have been assembled with anionic MXene (Zeta potential: -39.7 mV) to produce a superlattice-like heterostructure characteristic of a lateral size of around tens of nanometers, a surface area of 30 m2 g-1, and ultrathickness of several nanometers with repeated dimensions of 0.4 and 2.1 nm. Potential application of the synthesized Fe-N-C/MXene heterostructure has been demonstrated for electrocatalytic oxygen reduction reaction (ORR) that shows a positive onset potential of 0.92 V, four-electron transfer pathway, and strong durability of 20 h in alkaline electrolyte. This work suggests that metal clusters can assist the assembly of low-dimensional architectures for energy-related applications.

8.
ChemSusChem ; 13(7): 1730-1734, 2020 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-31943838

RESUMO

The activity and selectivity of simple photocatalysts for CO2 reduction remain limited by the insufficient photophysics of the catalysts, as well as the low solubility and slow mass transport of gas molecules in/through aqueous solution. In this study, these limitations are overcome by constructing a triphasic photocatalytic system, in which polymeric carbon nitride (CN) is immobilized onto a hydrophobic substrate, and the photocatalytic reduction reaction occurs at a gas-liquid-solid (CO2 -water-catalyst) triple interface. CN anchored onto the surface of a hydrophobic substrate exhibits an approximately 7.2-fold enhancement in total CO2 conversion, with a rate of 415.50 µmol m-2 h-1 under simulated solar light irradiation. This value corresponds to an overall photosynthetic efficiency for full water-CO2 conversion of 0.33 %, which is very close to biological systems. A remarkable enhancement of direct C2 hydrocarbon production and a high CO2 conversion selectivity of 97.7 % are observed. Going from water oxidation to phosphate oxidation, the quantum yield is increased to 1.28 %.

9.
Adv Mater ; : e1908140, 2020 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-31995254

RESUMO

Brilliance usually refers to the light reflected by the facets of a gemstone such as diamond due to its high refractive index. Nowadays, high-refractive-index materials find application in many optical and photonic devices and are mostly of inorganic nature. However, these materials are usually obtained by toxic or expensive production processes. Herein, the synthesis of a thin-film organic semiconductor, namely, polymeric carbon nitride, by thermal chemical vapor deposition is presented. Among polymers, this organic material combines the highest intrinsic refractive index reported so far with high transparency in the visible spectrum, even reaching the range of diamond. Eventually, the herein presented deposition of high quality thin films and their optical characteristics open the way for numerous new applications and devices in optics, photonics, and beyond based on organic materials.

10.
Langmuir ; 36(6): 1401-1408, 2020 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-31977224

RESUMO

Macromolecular crowding plays a critical role in the kinetics of enzymatic reactions. Dynamic compartmentalization of biological components in living cells due to liquid-liquid phase separation represents an important cell regulatory mechanism that can increase enzyme concentration locally and influence the diffusion of substrates. In the present study, we probed partitioning of two enzymes (horseradish-peroxidase and urate-oxidase) in a poly(ethylene glycol)-dextran aqueous two-phase system (ATPS) as a function of salt concentration and ion position in the Hofmeister series. Moreover, we investigated enzymatic cascade reactions and their kinetics within the ATPS, which revealed a strong influence of the ion hydration stemming from the background electrolyte on the partitioning coefficients of proteins following the Hofmeister series. As a result, we were able to realize cross-partitioning of two enzymes because of different protein net charges at a chosen pH. Our study reveals a strong dependency of the enzyme activity on the substrate type and crowding agent interaction on the final kinetics of enzymatic reactions in the ATPS and therefore provides substantial implications en route toward dynamic regulation of reactivity in synthetic protocells.

11.
Adv Mater ; 32(4): e1905399, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31803996

RESUMO

The emulation of human sensation, perception, and action processes has become a major challenge for bioinspired intelligent robotics, interactive human-machine interfacing, and advanced prosthetics. Reflex actions, enabled through reflex arcs, are important for human and higher animals to respond to stimuli from environment without the brain processing and survive the risks of nature. An artificial reflex arc system that emulates the functions of the reflex arc simplifies the complex circuit design needed for "central-control-only" processes and becomes a basic electronic component in an intelligent soft robotics system. An artificial somatic reflex arc that enables the actuation of electrochemical actuators in response to the stimulation of tactile pressures is reported. Only if the detected pressure by the pressure sensor is above the stimulus threshold, the metal-organic-framework-based threshold controlling unit (TCU) can be activated and triggers the electrochemical actuators to complete the motion. Such responding mechanism mimics the all-or-none law in the human nervous system. As a proof of concept, the artificial somatic reflex arc is successfully integrated into a robot to mimic the infant grasp reflex. This work provides a unique and simplifying strategy for developing intelligent soft robotics, next-generation human-machine interfaces, and neuroprosthetics.

12.
Angew Chem Int Ed Engl ; 58(52): 18813-18816, 2019 Dec 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.

13.
J Am Chem Soc ; 141(38): 14976-14980, 2019 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-31523954

RESUMO

The traditional NH3 production method (Haber-Bosch process) is currently complemented by electrochemical synthesis at ambient conditions, but the rather low selectivity (as indicated by the Faradaic efficiency) for the electrochemical reduction of molecular N2 into NH3 impedes the progress. Here, we present a powerful method to significantly boost the Faradaic efficiency of Au electrocatalysts to 67.8% for the nitrogen reduction reaction (NRR) by increasing their electron density through the construction of inorganic donor-acceptor couples of Ni and Au nanoparticles. The unique role of the electron-rich Au centers in facilitating the fixation and activation of N2 was also investigated via theoretical simulation methods and then confirmed by experimental results. The highly coupled Au and Ni nanoparticles supported on nitrogen-doped carbon are stable for reuse and long-term performance of the NRR, making the electrochemical process more sustainable for practical application.

14.
Macromolecules ; 52(13): 4989-4996, 2019 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-31543549

RESUMO

Metal-free graphitic carbon nitride (g-CN) has attracted significant attention recently due to its multiple applications, such as photocatalysis, energy storage and conversion, and biomaterials, albeit formation of g-CN films is challenging. Herein, a "grafting to" route to graft polymer brushes onto g-CN via visible-light irradiation is described. Afterward, g-CN/polymer films can be obtained through spin coating on glass substrates. As such, the present material provides an improved process toward further application of g-CN in thin films. Moreover, an improved dispersibility in organic solvent was realized after grafting and functional groups (such as epoxides) were introduced to g-CN. Subsequently, the epoxy groups were utilized for further functionalization to adjust the surface polarity.

15.
Nat Commun ; 10(1): 4380, 2019 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-31558716

RESUMO

Production of ammonia is currently realized by the Haber-Bosch process, while electrochemical N2 fixation under ambient conditions is recognized as a promising green substitution in the near future. A lack of efficient electrocatalysts remains the primary hurdle for the initiation of potential electrocatalytic synthesis of ammonia. For cheaper metals, such as copper, limited progress has been made to date. In this work, we boost the N2 reduction reaction catalytic activity of Cu nanoparticles, which originally exhibited negligible N2 reduction reaction activity, via a local electron depletion effect. The electron-deficient Cu nanoparticles are brought in a Schottky rectifying contact with a polyimide support which retards the hydrogen evolution reaction process in basic electrolytes and facilitates the electrochemical N2 reduction reaction process under ambient aqueous conditions. This strategy of inducing electron deficiency provides new insight into the rational design of inexpensive N2 reduction reaction catalysts with high selectivity and activity.

16.
Angew Chem Int Ed Engl ; 58(41): 14549-14555, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31418998

RESUMO

The photocatalytic CO2 reduction reaction (CRR) represents a promising route for the clean utilization of stranded renewable resources, but poor selectivity resulting from the competing hydrogen evolution reaction (HER) in aqueous solution limits its practical applicability. In the present contribution a photocatalyst with hydrophobic surfaces was fabricated. It facilitates an efficient three-phase contact of CO2 (gas), H2 O (liquid), and catalyst (solid). Thus, concentrated CO2 molecules in the gas phase contact the catalyst surface directly, and can overcome the mass-transfer limitations of CO2 , inhibit the HER because of lowering proton contacts, and overall enhance the CRR. Even when loaded with platinum nanoparticles, one of the most efficient HER promotion cocatalysts, the three-phase photocatalyst maintains a selectivity of 87.9 %. Overall, three-phase photocatalysis provides a general and reliable method to enhance the competitiveness of the CRR.

17.
Sci Total Environ ; 686: 1140-1151, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31412510

RESUMO

A novel preparation protocol for synthetic, look-a-like humic substances (i.e., fulvic and humic acids) simulating geochemical processes through hydrothermal reaction is presented, with crude waste biomass as an omnipresent and universal precursor. The chemical nature of the organic scaffold and the type and abundance of oxygen-containing functional groups of the synthetic humic substances (A-FA and A-HA) are revealed by a series of examinations. Results from EA, XPS analyze, FTIR spectra and NMR technology matched well each other, suggesting high similarity on chemical structure (abundant aromatic frameworks) and contents (e.g. N and S elements) in both humic acids. Pyrolysis-gas-chromatography/mass spectrometry (Py-GC/MS) analysis is employed on the organic structure and is directly compared to extracted natural humic matter from black soils (Harbin, China). Dehydrated carbohydrates and their condensates with low molecular weight that are rich in oxygen are the main structural components of the artificial fulvic acids, while aromatic structures and aliphatic side chains are almost absent. Aromatics (7.43%) and in some cases long-chain aliphatics (7.15%) are more prominent in the A-HA sample. The combination of the diverse analytical techniques not only allows a better understanding of artificial fulvic and humic acids, but also supports the high similarity to natural humic substances in structure and morphology. As the technology can be easily scaled and is comparable cheap, the as obtained products can be discussed to rehabilitate used up farm land.


Assuntos
Benzopiranos/análise , Poluição Ambiental/prevenção & controle , Recuperação e Remediação Ambiental/métodos , Substâncias Húmicas/análise , Eliminação de Resíduos/métodos , Resíduos Sólidos/análise , Biomassa , Solo
18.
Angew Chem Int Ed Engl ; 58(42): 14950-14954, 2019 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-31424624

RESUMO

Polymeric carbon nitride (PCN) is usually synthesized from nitrogen-rich monomers such as cyanamide, melamine, and urea, but is rather disordered in many cases. Now, a new allotrope of carbon nitride with internal heterostructures was obtained by co-condensation of very electron poor monomers (for example, 5-amino-tetrazole and nucleobases) in the presence of mild molten salts (for example, NaCl/KCl) to mediate the polymerization kinetics and thus modulate the local structure, charge carrier properties, and most importantly the HOMO and LUMO levels. Results reveal that the as-prepared NaK-PHI-A material shows excellent photo-redox activities because of a nanometric hetero-structure which enhances visible light absorption and promotes charge separation in the different domains.

19.
J Am Chem Soc ; 141(31): 12322-12328, 2019 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-31310113

RESUMO

Effective, solution-processable designs of interfacial electron-transporting layers (ETLs) or hole-blocking layers are promising tools in modern electronic devices, e.g., to improve the performance, cost, and stability of perovskite-based solar cells. Herein, we introduce a facile synthetic route of thiazole-modified carbon nitride with 1.5 nm thick nanosheets which can be processed to a homogeneous, metal-free ETL for inverted perovskite solar cells. We show that thiazole-modified carbon nitride enables electronic interface enhancement via suppression of charge recombination, achieving 1.09 V in Voc and a rise to 20.17 mA/cm2 in Jsc. Hence, this report presents the successful implementation of a carbon-nitride-based structure to boost charge extraction from the perovskite absorber toward the electron transport layer in p-i-n devices.

20.
Beilstein J Nanotechnol ; 10: 1316-1323, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31293868

RESUMO

A controllable ion transport including ion selectivity and ion rectification across nanochannels or porous membranes is of great importance because of potential applications ranging from biosensing to energy conversion. Here, a nanofluidic ion diode was realized by modifying carbon nitride nanotubes with different molecules yielding an asymmetric surface charge that allows for ion rectification. With the advantages of low-cost, thermal and mechanical robustness, and simple fabrication process, carbon nitride nanotubes with ion rectification have the potential to be used in salinity-gradient energy conversion and ion sensor systems.

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