Journal of Physical Chemistry. C, Nanomaterials and Interfaces

Defects in the crystal structures of metal-organic frameworks (MOFs), whether present intrinsically or introduced via so-called defect engineering, can play strong roles in the properties of MOFs for various applications. Unfortunately, direct experimental detection and characterization of defects in MOFs are very challenging. We show that in many cases, the differences between experimentally observed and computationally predicted water stabilities of MOFs can be used to deduce information on the presence of point defects in real materials...

All-inorganic halide perovskites have received a great deal of attention as attractive alternatives to overcome the stability issues of hybrid halide perovskites that are commonly associated with organic cations. To find a compromise between the optoelectronic properties of CsPbI3 and CsPbBr3 , perovskites with CsPb(Br x I1- x )3 mixed compositions are commonly used. An additional benefit is that without sacrificing the optoelectronic properties for applications such as solar cells or light-emitting diodes, small amounts of Br in CsPbI3 can prevent the inorganic perovskite from degrading to a photo-inactive non-perovskite yellow phase...

Efforts to study intricate, higher-order cellular functions have called for fluorescence imaging under physiologically relevant conditions such as tissue systems in simulated native buffers. This endeavor has presented novel challenges for fluorescent probes initially designed for use in simple buffers and monolayer cell culture. Among current fluorescent probes, semiconductor nanocrystals, or quantum dots (QDs), offer superior photophysical properties that are the products of their nanoscale architectures and chemical formulations...

Films of titania-supported monometallic Pd, Pt, and bimetallic Pt-Pd catalysts made of metallic nanoparticles were prepared by magnetron sputtering and studied in the oxidative dehydrogenation (ODH) of cyclohexene. Pd/TiO x and Pt-Pd/TiO x were found active at as low temperature as 150 °C and showed high catalytic activity with high conversion (up to 81%) and benzene selectivity exceeding 97% above 200 °C. In turn, the Pt/TiO x catalyst performed poorly with the onset of benzene production at 200 °C only and conversions not exceeding 5%...

Developing biocompatible nanocoatings is crucial for biomedical applications. Noble metal colloidal nanoparticles with biomolecular shells are thought to combine diverse chemical and optothermal functionalities with biocompatibility. Herein, we present nanoparticles with peptide hydrogel shells that feature an unusual combination of properties: the metal core possesses localized plasmon resonance, whereas a few-nanometer-thick shells open opportunities to employ their soft framework for loading and scaffolding...

A fundamental understanding of proton transport through graphene nanopores, defects, and vacancies is essential for advancing two-dimensional proton exchange membranes (PEMs). This study employs ReaxFF molecular dynamics, metadynamics, and density functional theory to investigate the enhanced proton transport through a graphene nanopore. Covalently functionalizing the nanopore with a benzenesulfonic group yields consistent improvements in proton permeability, with a lower activation barrier (≈0.15 eV) and increased proton selectivity over sodium cations...

The investigation of precursor classes for the fabrication of nanostructures is of specific interest for maskless fabrication and direct nanoprinting. In this study, the differences in material composition depending on the employed process are illustrated for focused-ion-beam- and focused-electron-beam-induced deposition (FIBID/FEBID) and compared to the thermal decomposition in chemical vapor deposition (CVD). This article reports on specific differences in the deposit composition and microstructure when the (H3 Si)2 Fe(CO)4 precursor is converted into an inorganic material...

Single-atom catalysts (SACs) of embedding an active metal in nitrogen-doped graphene are emergent catalytic materials in various applications. The rational design of efficient SACs necessitates an electronic and mechanistic understanding of those materials with reliable quantum mechanical simulations. Conventional computational methods of modeling SACs involve using an infinite slab model with periodic boundary condition, limiting to the selection of generalized gradient approximations as the exchange correlation (XC) functional within density functional theory (DFT)...

Despite the common expectation that conjugated organic molecules on metals adsorb in a flat-lying layer, several recent studies have found coverage-dependent transitions to upright-standing phases, which exhibit notably different physical properties. In this work, we argue that from an energetic perspective, thermodynamically stable upright-standing phases may be more common than hitherto thought. However, for kinetic reasons, this phase may often not be observed experimentally. Using first-principles kinetic Monte Carlo simulations, we find that the structure with lower molecular density is (almost) always formed first, reminiscent of Ostwald's rule of stages...

Propane dehydrogenation (PDH) is an on-purpose catalytic technology to produce propylene from propane that operates at high temperatures, 773-973 K. Several key industry players have been active in developing new catalysts and processes with improved carbon footprint and economics, where Pt-based catalysts have played a central role. The optimization of these catalytic systems through computational and atomistic simulations requires large-scale models that account for their reactivity and dynamic properties...

The local microenvironment has recently been found to play a major role in the electrocatalytic activity of nanomaterials. Modulating the microenvironment by adding alkali metal cations into the electrolyte can be used to either suppress hydrogen or oxygen evolution, thereby extending the electrochemical window of energy storage systems, or to tune the selectivity of electrocatalysts. MXenes are a large family of two-dimensional transition metal carbides, nitrides, and carbonitrides that have shown potential for use in electrochemical energy storage applications...

The ability to directly monitor the states of electrons in modern field-effect transistors (FETs) could transform our understanding of the physics and improve the function of related devices. In particular, phosphorene allotropes present a fertile landscape for the development of high-performance FETs. Using density functional theory-based methods, we have systematically investigated the influence of electrostatic gating on the structures, stabilities, and fundamental electronic properties of pristine and carbon-doped monolayer (bilayer) phosphorene allotropes...

Anion engineering has proven to be an effective strategy to tailor the physical and chemical properties of metal oxides by modifying their existing crystal structures. In this work, a low-temperature synthesis for rare earth (RE)-doped Y2 O2 SO4 and Y2 O2 S was developed via annealing of Y(OH)3 intermediates in the presence of elemental sulfur in a sealed tube, followed by a controlled reduction step. The crystal structure patterns (X-ray diffraction) and optical spectra (UV-IR) of Y2 O2 SO4 , Y2 O2 S, and crystalline Y2 O3 were collected throughout the treatment steps to correlate the structural transformations (via thermogravimetric analysis) with the optical properties...

The time evolution of the exciton generated by light adsorption in a photocatalyst is an important feature that can be approached from full nonadiabatic molecular dynamics simulations. Here, a crucial parameter is the nonradiative recombination rate between the hole and the electron that form the exciton. In the present work, we explore the performance of a Fermi's golden rule-based approach on predicting the recombination rate in a set of photoactive titania nanostructures, relying solely on the coupling of the ground and first excited state...

Classical electrochemical and microscopy methods were used to characterize the interfacial processes of the adsorption of chloride ions from ionic liquids at the Bi(111) single crystal electrode. The mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium chloride was electrochemically characterized by using cyclic voltammetry and electrochemical impedance spectroscopy. In situ scanning tunneling microscopy images showed the formation of superstructures at the electrode's surface over an extended period of time...

Poly( p -phenylenevinylene) (PPV) is a staple of the family of conjugated polymers with desirable optoelectronic properties for applications including light-emitting diodes (LEDs) and photovoltaic devices. Although the significant impact of olefin geometry on the steady-state optical properties of PPVs has been extensively studied, PPVs with precise stereochemistry have yet to be investigated using nonlinear optical spectroscopy for quantum sensing, as well as light harvesting for biological applications. Herein, we report our investigation of the influence of olefin stereochemistry on both linear and nonlinear optical properties through the synthesis of all- cis and all- trans PPV copolymers...

Perfluorooctanoic acid (PFOA) is an environmentally prevalent and persistent organic pollutant with toxic and bioaccumulative properties. Despite the known importance of perfluorinated pollutants in the global environment, molecular-level details of the physicochemical behavior of PFOA on aqueous interfaces remain poorly understood. Here, we utilized two surface-specific techniques, vibrational sum frequency generation spectroscopy (SFG) and surface tensiometry, to investigate the pH-induced structural changes of PFOA and octanoic acid (OA) and determined the apparent p K a at the air-water surface...

Oxygen defects in semiconducting single-walled carbon nanotubes (SWCNTs) are localized disruptions in the carbon lattice caused by the formation of epoxy or ether groups, commonly through wet-chemical reactions. The associated modifications of the electronic structure can result in luminescent states with emission energies below those of pristine SWCNTs in the near-infrared range, which makes them promising candidates for applications in biosensing and as single-photon emitters. Here, we demonstrate the controlled introduction of luminescent oxygen defects into networks of monochiral (6,5) SWCNTs using a solid-state photocatalytic approach...

Inversion analysis of transient absorption data to capture the photoexcited charge carrier population rate dynamics is a powerful technique for extracting realistic lifetimes and identifying recombination pathways. However, for highly scattering samples such as Cu2 O nanoparticles (NPs) with associated dielectric Mie scattering, the scattering leads to an inaccurate measure of the excited photocarrier. This work studies methods to correct for the scattering to generalize the use of inversion analysis and provide secondary information about the nature of the scattering NPs...

In this work, we present a first-principles investigation of the properties of superlattices made from transition metal dichalcogenides for use as electrodes in lithium-ion and magnesium-ion batteries. From a study of 50 pairings, we show that, in general, the volumetric expansion, intercalation voltages, and thermodynamic stability of vdW superlattice structures can be well approximated with the average value of the equivalent property for the component layers. We also found that the band gap can be reduced, improving the conductivity...