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1.
Ultramicroscopy ; 262: 113978, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38692141

RESUMO

In this work we instigated the fragmentation of Au microparticles supported on a thin amorphous carbon film by irradiating them with a gradually convergent electron beam inside the Transmission Electron Microscope. This phenomenon has been generically labeled as "electron beam-induced fragmentation" or EBIF and its physical origin remains contested. On the one hand, EBIF has been primarily characterized as a consequence of beam-induced heating. On the other, EBIF has been attributed to beam-induced charging eventually leading to Coulomb explosion. To test the feasibility of the charging framework for EBIF, we instigated the fragmentation of Au particles under two different experimental conditions. First, with the magnetic objective lens of the microscope operating at full capacity, i.e. background magnetic field B=2 T, and with the magnetic objective lens switched off (Lorenz mode), i.e. B=0 T. We observe that the presence or absence of the magnetic field noticeably affects the critical current density at which EBIF occurs. This strongly suggests that magnetic field effects play a crucial role in instigating EBIF on the microparticles. The dependence of the value of the critical current density on the absence or presence of an ambient magnetic field cannot be accounted for by the beam-induced heating model. Consequently, this work presents robust experimental evidence suggesting that Coulomb explosion driven by electrostatic charging is the root cause of EBIF.

2.
ACS Appl Bio Mater ; 7(2): 839-852, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38253353

RESUMO

Implant-related infections or inflammation are one of the main reasons for implant failure. Therefore, different concepts for prevention are needed, which strongly promote the development and validation of improved material designs. Besides modifying the implant surface by, for example, antibacterial coatings (also implying drugs) for deterring or eliminating harmful bacteria, it is a highly promising strategy to prevent such implant infections by antibacterial substrate materials. In this work, the inherent antibacterial behavior of the as-cast biodegradable Fe69Mn30C1 (FeMnC) alloy against Gram-negative Pseudomonas aeruginosa and Escherichia coli as well as Gram-positive Staphylococcus aureus is presented for the first time in comparison to the clinically applied, corrosion-resistant AISI 316L stainless steel. In the second step, 3.5 wt % Cu was added to the FeMnC reference alloy, and the microbial corrosion as well as the proliferation of the investigated bacterial strains is further strongly influenced. This leads for instance to enhanced antibacterial activity of the Cu-modified FeMnC-based alloy against the very aggressive, wild-type bacteria P. aeruginosa. For clarification of the bacterial test results, additional analyses were applied regarding the microstructure and elemental distribution as well as the initial corrosion behavior of the alloys. This was electrochemically investigated by a potentiodynamic polarization test. The initial degraded surface after immersion were analyzed by glow discharge optical emission spectrometry and transmission electron microscopy combined with energy-dispersive X-ray analysis, revealing an increase of degradation due to Cu alloying. Due to their antibacterial behavior, both investigated FeMnC-based alloys in this study are attractive as a temporary implant material.


Assuntos
Ligas , Próteses e Implantes , Ligas/química , Antibacterianos/farmacologia , Antibacterianos/química
3.
Materials (Basel) ; 16(5)2023 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-36903058

RESUMO

In this study, a newly developed high-strength cast Fe81Cr15V3C1 (wt%) steel with a high resistance against dry abrasion and chloride-induced pitting corrosion is presented. The alloy was synthesized through a special casting process that yielded high solidification rates. The resulting fine, multiphase microstructure is composed of martensite, retained austenite and a network of complex carbides. This led to a very high compressive strength (>3800 MPa) and tensile strength (>1200 MPa) in the as-cast state. Furthermore, a significantly higher abrasive wear resistance in comparison to the conventional X90CrMoV18 tool steel was determined for the novel alloy under very harsh wear conditions (SiC, α-Al2O3). Regarding the tooling application, corrosion tests were conducted in a 3.5 wt.% NaCl solution. Potentiodynamic polarization curves demonstrated a similar behavior during the long-term testing of Fe81Cr15V3C1 and the X90CrMoV18 reference tool steel, though both steels revealed a different nature of corrosion degradation. The novel steel is less susceptible to local degradation, especially pitting, due to the formation of several phases that led to the development of a less dangerous form of destruction: galvanic corrosion. In conclusion, this novel cast steel offers a cost- and resource-efficient alternative to conventionally wrought cold-work steels, which are usually required for high-performance tools under highly abrasive as well as corrosive conditions.

4.
Materials (Basel) ; 15(20)2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-36295338

RESUMO

A high-performance tool steel with the nominal composition Fe85Cr4Mo8V2C1 (wt%) was processed by three different manufacturing techniques with rising cooling rates: conventional gravity casting, centrifugal casting and an additive manufacturing process, using laser powder bed fusion (LPBF). The resulting material of all processing routes reveals a microstructure, which is composed of martensite, austenite and carbides. However, comparing the size, the morphology and the weight fraction of the present phases, a significant difference of the gravity cast samples is evident, whereas the centrifugal cast material and the LPBF samples show certain commonalities leading finally to similar mechanical properties. This provides the opportunity to roughly estimate the mechanical properties of the material fabricated by LPBF. The major benefit arises from the required small material quantity and the low resources for the preparation of samples by centrifugal casting in comparison to the additive manufacturing process. Concluding, the present findings demonstrate the high attractiveness of centrifugal casting for the effective material screening and hence development of novel alloys adapted to LPBF-processing.

5.
Nanoscale ; 14(29): 10483-10492, 2022 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-35822883

RESUMO

Solid solutions of 2D transition metal trihalides are rapidly growing in interest for the search for new 2D materials with novel properties at nanoscale dimensions. In this regard, we present a synthesis method for the Cr1-xRuxCl3 solid solution and describe the behaviour of the unit cell parameters over the whole composition range, which in general follows Vegard's law in the range of a = 5.958(6)CrCl3 … 5.9731(5)RuCl3 Å, b = 10.3328(20)CrCl3 … 10.34606(21)RuCl3 Å, c = 6.110(5)CrCl3 … 6.0385(5)RuCl3 Å and ß = 108.522(15)CrCl3 … 108.8314(14)RuCl3 °. The synthesized solid solution powder was subsequently used to deposit micro- and nanosheets directly on a substrate by applying chemical vapour transport in a temperature gradient of 575 °C → 525 °C for 2 h and 650 °C → 600 °C for 0.5 h as a bottom-up approach without the need for an external transport agent. The observed chromium chloride enrichment of the deposited crystals is predicted by thermodynamic simulation. The results allow for a nanostructure synthesis of this solid solution with a predictable composition down to about 30 nm in height and lateral size of several µm. When applying a quick consecutive delamination step, it is possible to obtain few- and monolayer structures, which could be used for further studies of downscaling effects for the CrCl3-RuCl3 solid solution. X-ray photoelectron spectroscopy, transmission electron microscopy and Raman spectroscopy were used to confirm the purity and quality of the synthesized crystals.

6.
Small ; 17(33): e2102045, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-34235845

RESUMO

Thermal management is of vital importance in various modern technologies such as portable electronics, photovoltaics, and thermoelectric devices. Impeding phonon transport remains one of the most challenging tasks for improving the thermoelectric performance of certain materials such as half-Heusler compounds. Herein, a significant reduction of lattice thermal conductivity (κL ) is achieved by applying a pressure of ≈1 GPa to sinter a broad range of half-Heusler compounds. Contrasting with the common sintering pressure of less than 100 MPa, the gigapascal-level pressure enables densification at a lower temperature, thus greatly modifying the structural characteristics for an intensified phonon scattering. A maximum κL reduction of ≈83% is realized for HfCoSb from 14 to 2.5 W m-1 K-1 at 300 K with more than 95% relative density. The realized low κL originates from a remarkable grain-size refinement to below 100 nm together with the abundant in-grain defects, as determined by microscopy investigations. This work uncovers the phonon transport properties of half-Heusler compounds under unconventional microstructures, thus showing the potential of high-pressure compaction in advancing the performance of thermoelectric materials.

7.
ACS Appl Mater Interfaces ; 12(48): 53827-53840, 2020 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-33201669

RESUMO

Electrode materials with a high performance and stable cycling have been commercialized, but the utilization of state-of-the-art Li-ion batteries in high-current rate applications is restricted because of limitations in other battery components, in particular, the lack of an efficient binder. Herein, a novel multicomponent polymer gel binder (PGB) is presented, comprising the biopolymer chitosan as the host, embedded with the 1-butyl-1-methylpyrrolidinium dicyanamide (PYR14DCA) ionic liquid and the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The multicomponent approach leads to carbon black arrangement along well-distributed chitosan chains in the electrodes, forming a highly electronic conductive network. Furthermore, the plasticizing effect of the ionic liquid leads to an enhanced ionic conductivity. As a result, shorter charge-transfer paths are enabled, leading to an exceptionally high rate capability in LiFePO4 and Li4Ti5O12 half cells, up to 50C. LiFePO4||Li4Ti5O12 full cells using the PGB for both electrodes also demonstrated stable cycling at 10C, with an impressively high discharge capacity of 173 mA h·g-1 after 1000 cycles. In addition, freestanding electrodes could also be realized and functioning flexible Li-ion cells were successfully demonstrated. Thus, the novel water-processable binder offers multifaceted advantages, making the approach highly promising for industrial implementation.

8.
Mater Sci Eng C Mater Biol Appl ; 117: 111305, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32919666

RESUMO

The present work introduces combination of superparamagnetic iron oxides (SPIONs) and hexamolybdenum cluster ([{Mo6I8}I6]2-) units within amino-decorated silica nanoparticles (SNs) as promising design of the hybrid SNs as efficient cellular contrast and therapeutic agents. The heating generated by SNs doped with SPIONs (Fe3O4@SNs) under alternating magnetic field is characterized by high specific absorption rate (SAR = 446 W/g). The cluster units deposition onto both Fe3O4@SNs and "empty" silica nanoparticles (SNs) results in Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6] with red cluster-centered luminescence and ability to generate reactive oxygen species (ROS) under the irradiation. The monitoring of spin-trapped ROS by ESR spectroscopy technique indicates that the ROS-generation decreases in time for SNs[{Mo6I8}I6] and [{Mo6I8}I6]2- in aqueous solutions, while it remains constant for Fe3O4@SNs[{Mo6I8}I6]. The cytotoxicity is low for both Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6], while the flow cytometry indicates preferable cellular uptake of the former versus the latter type of the nanoparticles. Moreover, entering into nucleus along with cytoplasm differentiates the intracellular distribution of Fe3O4@SNs[{Mo6I8}I6] from that of SNs[{Mo6I8}I6], which remain in the cell cytoplasm only. The exceptional behavior of Fe3O4@SNs[{Mo6I8}I6] is explained by residual amounts of iron ions at the silica surface.


Assuntos
Nanopartículas de Magnetita , Nanopartículas , Ferro , Luminescência , Espécies Reativas de Oxigênio , Dióxido de Silício
9.
Nanoscale ; 11(34): 16103-16113, 2019 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-31432850

RESUMO

This report introduces both synthesis and in vitro biological behaviour of dual magnetic-fluorescent silica nanoparticles. The amino group-decoration of 78 nm sized silica nanoparticles enables their efficient internalization into motoneurons, which is visualized by the red fluorescence arising from [Ru(dipy)3]2+ complexes encapsulated into a silica matrix. The internalized nanoparticles are predominantly located in the cell cytoplasm as revealed by confocal microscopy imaging. The magnetic function of the nanoparticles resulted from the incorporation of 17 nm sized superparamagnetic iron oxide cores into the silica matrix, enabling their responsivity to magnetic fields. Fluorescence analysis revealed the "on-off" switching of Ca2+ influx under the application and further removal of the permanent magnetic field. This result for the first time highlights the movement of the nanoparticles within the cell cytoplasm in the permanent magnetic field as a promising tool to enhance the neuronal activity of motoneurons.

10.
Chemistry ; 25(26): 6562-6568, 2019 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-30900781

RESUMO

Cyano-substituted polyphenylene vinylenes (PPVs) have been the focus of research for several decades owing to their interesting optoelectronic properties and potential applications in organic electronics. With the advent of organic two-dimensional (2D) crystals, the question arose as to how the chemical and optoelectronic advantages of PPVs evolve in 2D compared with their linear counterparts. In this work, we present the efficient synthesis of two novel 2D fully sp2 -carbon-linked crystalline PPVs and investigate the essentiality of inorganic bases for their catalytic formation. Notably, among all bases screened, cesium carbonate (Cs2 CO3 ) plays a crucial role and enables reversibility in the first step with subsequent structure locking by formation of a C=C double bond to maintain crystallinity, which is supported by density functional theory (DFT) calculations. A quantifiable energy diagram of a "quasi-reversible reaction" is proposed, which allows the identification of further suitable C-C bond formation reactions for 2D polymerizations. Moreover, the narrowing of the HOMO-LUMO gap is delineated by expanding the conjugation into two dimensions. To enable environmentally benign processing, the post-modification of 2D PPVs is further performed, which renders stable dispersions in the aqueous phase.

11.
ChemSusChem ; 12(1): 310-319, 2019 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-30303617

RESUMO

Nitrogen-doped carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis by using renewable biomass waste. Three solid materials are used: sawdust as a carbon source, urea and/or melamine as a nitrogen source, and potassium carbonate as an activation agent. The resulting nitrogen-doped porous carbons offer a very high specific surface area of up to 3000 m2 g-1 and a large pore volume up to 2 cm3 g-1 . Also, a high nitrogen content of 4 wt % (urea only) up to 12 wt % (melamine only) is generated, depending on the nitrogen and carbon sources. The mechanochemical reaction and the impact of different wood components on the porosity and surface functionalities are investigated by nitrogen physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). These N-doped carbons are highly suitable as cathode materials for Li-S batteries, showing high initial discharge capacities of up to 1300 mAh gsulfur -1 (95 % coulombic efficiency) and >75 % capacity retention within the first 50 cycles at low electrolyte volume.

12.
Sci Rep ; 8(1): 15400, 2018 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-30337612

RESUMO

Superhierarchically rough films are rapidly synthesised on metal substrates via electrochemically triggered self-assembly of meso/macroporous-structured metal-organic framework (MOF) crystals. These coatings are applied to immobilise a functional oil with low surface energy to provide stable coatings repellent to a wide range of hydrophobic as well as hydrophilic fluids. Such omniphobic surfaces are highly interesting for several applications such as anti-fouling, anti-icing, and dropwise condensation, and become easily scalable with the presented bottom-up fabrication approach. As investigated by environmental scanning electron microscopy (ESEM), the presented perfluorinated oil-infused Cu-BTC coating constitutes of a flat liquid-covered surface with protruding edges of octahedral superstructured MOF crystals. Water and non-polar diiodomethane droplets form considerably high contact angles and even low-surface-tension fluids, e.g. acetone, form droplets on the infused coating. The repellent properties towards the test fluids do not change upon extended water spraying in contrast to oil-infused porous copper oxide or native copper surfaces. It is discussed in detail, how the presented electrodeposited MOF films grow and provide a proficient surface morphology to stabilise the functional oil film due to hemiwicking.

13.
ACS Appl Mater Interfaces ; 10(42): 36108-36119, 2018 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-30251827

RESUMO

Two new structural forms of Na xCo0.5Ti0.5O2, the layered O3- and P3-forms, were synthesized and comprehensively characterized. Both materials show electrochemical activity as electrodes in Na-ion batteries. During cell charging (desodiation of the Na xCo0.5Ti0.5O2 cathode), we observed a structural phase transformation of O3-Na0.95Co0.5Ti0.5O2 into P3-Na xCo0.5Ti0.5O2, whereas no changes other than conventional unit cell volume shrinkage were detected for P3-Na0.65Co0.5Ti0.5O2. During Na insertion (cell discharging), the reconversion of the P3-form into O3-Na xCo0.5Ti0.5O2 was impeded for both materials and occurs well below 1 V versus Na+/Na only. The reconversion is hindered by the charge and spin transfers of Co (LS-Co3+ → HS-Co2+) and by a significant unit cell volume expansion at the P3 → O3 transformation, as revealed from the magnetization, crystallographic, and spectroscopic studies. As the kinetics of such transformations depend on numerous parameters such as time, temperature, and particle size, a large cell overpotential ensues. An extended cutoff voltage at 0.2 V versus Na+/Na during discharging allows to complete the P3 → O3 transformation and increases the specific discharging capacity to 200 mA h g-1. Moreover, a quasi-symmetrical full cell, based on the O3- and P3-forms, was designed, eliminating safety concerns associated with sodium anodes and delivering a discharge capacity of 130 mA h g-1.

14.
Inorg Chem ; 57(12): 7201-7207, 2018 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-29808682

RESUMO

Two novel compounds, LiCu Ch ( Ch = Se or Te), were synthesized by direct reaction between elements in closed ampules inside corundum crucibles. Both compounds are highly air-sensitive and possess an anti-PbClF crystal structure, which contains Cu Ch layer analogues to the Fe[As/Se] layers in Fe-based superconductors. In electrochemical battery cells, Li can be almost completely extracted from LiCuSe, but the reverse reaction is only partly successful and Li2Se and Cu2- xSe are formed instead. LiCuSe exhibits a temperature independent and slightly positive magnetic susceptibility. From 7Li NMR measurements, the activation energy of the Li ion diffusion process is about 0.5 eV but is slightly lower for LiCuTe as compared to LiCuSe. Also, the small and almost temperature independent NMR shifts of the 7Li nucleus indicate the absence of Pauli paramagnetism in these compounds, consistent with a 3 d10 full valence state of the Cu ions.

15.
ACS Appl Mater Interfaces ; 10(8): 7096-7106, 2018 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-29384653

RESUMO

The electrochemical characteristics of silicon diphosphide (SiP2) as a new anode material for future lithium-ion batteries (LIBs) are evaluated. The high theoretical capacity of about 3900 mA h g-1 (fully lithiated state: Li15Si4 + Li3P) renders silicon diphosphide as a highly promising candidate to replace graphite (372 mA h g-1) as the standard anode to significantly increase the specific energy density of LIBs. The proposed mechanism of SiP2 is divided into a conversion reaction of phosphorus species, followed by an alloying reaction forming lithium silicide phases. In this study, we focus on the conversion mechanism during cycling and report on the phase transitions of SiP2 during lithiation and delithiation. By using ex situ analysis techniques such as X-ray powder diffraction, formed reaction products are identified. Magic angle spinning nuclear magnetic resonance spectroscopy is applied for the characterization of long-range ordered compounds, whereas X-ray photoelectron spectroscopy gives information of the surface-layer species at the interface of active material and electrolyte. Our SiP2 anode material shows a high initial capacity of about 2700 mA h g-1, whereas a fast capacity fading during the first few cycles occurs which is not necessarily expected. On the basis of our results, we conclude that besides other degradation effects, such as electrolyte decomposition and electrical contact loss, the rapid capacity fading originates from the formation of a low ion-conductive layer of LiP. This insulating layer hinders lithium-ion diffusion during lithiation and thereby mainly contributes to fast capacity fading.

16.
Materials (Basel) ; 10(6)2017 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-28773032

RESUMO

TiO2 nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li⁺ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO2/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li⁺ ion diffusivity, promoting a strongly favored lithium insertion into the TiO2/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability.

17.
ACS Appl Mater Interfaces ; 9(21): 18015-18021, 2017 May 31.
Artigo em Inglês | MEDLINE | ID: mdl-28485974

RESUMO

One of the challenges in obtaining hydrogen economically by electrochemical water splitting is to identify and substitute cost-effective earth-abundant materials for the traditionally used precious-metal-based water-splitting electrocatalysts. Herein, we report the electrochemical formation of a thin film of nickel-based Prussian blue analogue hexacyanoferrate (Ni-HCF) through the anodization of a nickel substrate in ferricyanide electrolyte. As compared to the traditionally used Nafion-binder-based bulk film, the anodically obtained binder-free Ni-HCF film demonstrates superior performance in the electrochemical hydrogen evolution reaction (HER), which is highly competitive with that shown by a Pt-plate electrode. The HER onset and the benchmark cathodic current density of 10 mA cm-2 were achieved at small overpotentials of 15 mV and 0.2 V (not iR-corrected), respectively, in 1 M KOH electrolyte, together with the long-term electrochemical durability of the film. Further, a metal-HCF-electrode-based full water-splitting device consisting of the binder-free Ni-HCF film on a Ni plate and a one-dimensional Co-HCF film on carbon paper as the electrodes for the HER and the oxygen evolution reaction (OER), respectively, was designed and was found to demonstrate very promising performance for overall water splitting.

18.
ChemSusChem ; 10(11): 2416-2424, 2017 06 09.
Artigo em Inglês | MEDLINE | ID: mdl-28436604

RESUMO

Nitrogen-doped nanoporous carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis. This facile approach involves the mechanochemical treatment and carbonization of three solid materials: potassium carbonate, urea, and lignin, which is a waste product from pulp industry. The resulting nitrogen-doped porous carbons offer a very high specific surface area up to 3000 m2 g-1 and large pore volume up to 2 cm3 g-1 . The mechanochemical reaction and the impact of activation and functionalization are investigated by nitrogen and water physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). Our N-doped carbons are highly suitable for electrochemical energy storage as supercapacitor electrodes, showing high specific capacitances in aqueous 1 m Li2 SO4 electrolyte (177 F g-1 ), organic 1 m tetraethylammonium tetrafluoroborate in acetonitrile (147 F g-1 ), and an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate; 192 F g-1 ). This new mechanochemical pathway synergistically combines attractive energy-storage ratings with a scalable, time-efficient, cost-effective, and environmentally favorable synthesis.


Assuntos
Carbono/química , Capacitância Elétrica , Carbonatos/química , Eletrodos , Eletrólitos/química , Lignanas/química , Nanoporos , Nitrogênio/química , Potássio/química , Ureia/química
19.
ACS Appl Mater Interfaces ; 9(15): 12930-12935, 2017 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-28374990

RESUMO

This work reports on designing of first successful MOF-sensitizer based solid-state photovoltaic device, perticularly with a meaningful output power conversion efficiency. In this study, an intrinsically conductive cobalt-based MOFs (Co-DAPV) formed by the coordination between Co (II) ions and a redox active di(3-diaminopropyl)-viologen (i.e., DAPV) ligand is investigated as sensitizer. Hall-effect measurement shows p-type conductivity of the Co-DAPV film with hole mobility of 0.017 cm2 V-1 s-1, suggesting its potential application as hole transporting sensitizer. Further, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of Co-DAPV are well-matched to be suitably employed for sensitizing TiO2. Thus, by layer-by-layer deposition of hole conducting MOF-sensitizer onto mesoporous TiO2 film, a power conversion efficiency of as high as 2.1% is achieved, which exceeds the highest efficiency values of MOF-sensitized liquid-junction solar cells reported so far.

20.
ACS Nano ; 11(2): 1946-1956, 2017 02 28.
Artigo em Inglês | MEDLINE | ID: mdl-28117971

RESUMO

To synthesize graphene by chemical vapor deposition (CVD) both in large area and with uniform layer number directly over Si/SiOx has proven challenging. The use of catalytically active metal substrates, in particular Cu, has shown far greater success and therefore is popular. That said, for electronics applications it requires a transfer procedure, which tends to damage and contaminate the graphene. Thus, the direct fabrication of uniform graphene on Si/SiOx remains attractive. Here we show a facile confinement CVD approach in which we simply "sandwich" two Si wafers with their oxide faces in contact to form uniform monolayer graphene. A thorough examination of the material reveals it comprises faceted grains despite initially nucleating as round islands. Upon clustering, they facet to minimize their energy. This behavior leads to faceting in polygons, as the system aims to ideally form hexagons, the lowest energy form, much like the hexagonal cells in a beehive, which requires the minimum wax. This process also leads to a near minimal total grain boundary length per unit area. This fact, along with the high graphene quality, is reflected in its electrical performance, which is highly comparable with graphene formed over other substrates, including Cu. In addition, the graphene growth is self-terminating. Our CVD approach is easily scalable and will make graphene formation directly on Si wafers competitive against that from metal substrates, which suffer from transfer. Moreover, this CVD route should be applicable for the direct synthesis of other 2D materials and their van der Waals heterostructures.

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