Journal of Physical Chemistry. C, Nanomaterials and Interfaces

Within computational heterogeneous catalysis, two critical factors exist-coverage and multifaceted effects-which are challenging to incorporate and contribute to differences between the results obtained from computational and experimental studies. Such disparities exist when significant adsorbate-adsorbate interactions are present, particularly when coupled with computationally limited facet sampling. Here, we designed a study to demonstrate the significance of coverage and facet effects on the predicted coverages for O* and H* on Pt nanoparticles...

The complex interplay between local chemistry, the solvent microenvironment, and electrified interfaces frequently present in electrocatalytic reactions has motivated the development of quantum chemical methods that can accurately model these effects. Here, we predict the thermodynamics of the nitrogen reduction reaction (NRR) at sulfur vacancies in 1T'-phase MoS2 and highlight how the realistic treatment of potential within grand canonical density functional theory (GC-DFT) seamlessly captures the multiple competing effects of applied potential on a catalyst interface interacting with solvated molecules...

Conventional non-fullerene acceptors (NFAs) typically have planar structures that can enable improved electron mobility and produce more efficient organic photovoltaic devices. A relatively simple A-D-A'-D-A type NFA specifically designed to match with poly(3-hexylthiophene-2,5-diyl) (P3HT) for green-absorbing agrivoltaic applications has been examined using a variety of techniques: microsecond transient absorption spectroscopy, atomic force microscopy, and photoluminescence. Relatively invariant charge carrier decay dynamics are observed in the blend films across a variety of processing solvents...

The properties of MXene flakes, a new class of two-dimensional materials, are strictly determined by their surface termination. The most common termination groups are oxygen-containing (=O or -OH) and fluorine (-F), and their relative ratio is closely related to flake stability and catalytic activity. The surface termination can vary significantly among MXene flakes depending on the preparation route and is commonly determined after flake preparation by using X-ray photoelectron spectroscopy (XPS). In this paper, as an alternative approach, we propose the combination of surface-enhanced Raman spectroscopy (SERS) and artificial neural networks (ANN) for the precise and reliable determination of MXene flakes' (Ti3 C2 T x ) surface chemistry...

A series of steady-state and time-resolved spectroscopies were performed on a set of eight carbene-metal-amide (cMa) complexes, where M = Cu and Au, that have been used as photosensitizers for photosensitized electrocatalytic reactions. Using ps-to-ns and ns-to-ms transient absorption spectroscopies (psTA and nsTA, respectively), the excited-state kinetics from light absorption, intersystem crossing (ISC), and eventually intermolecular charge transfer were thoroughly characterized. Using time-correlated single photon counting (TCSPC) and psTA with a thermally activated delayed fluorescence (TADF) model, the variation in intersystem crossing (ISC), ( S 1 → T 1 ) rates (∼3-120 × 109 s-1 ), and Δ E ST values (73-115 meV) for these compounds were fully characterized, reflecting systematic changes to the carbene, carbazole, and metal...

Concentrated and thick oil-in-water nanoemulsions have been observed to become more transparent with increasing oil volume fraction. This study demonstrates rigorously experimentally and numerically that such unusual behavior is due to dependent scattering including not only far-field but also near-field effects. Indeed, when the droplet concentration is sufficiently large, their interparticle distance becomes small compared to the wavelength of light and scattering by a given droplet may be affected by the proximity of others...

Conjugated polymers composed of alternating electron donor and acceptor segments have come to dominate the materials being considered for organic photoelectrodes and solar cells, in large part because of their favorable near-infrared absorption. The prototypical electron-transporting push-pull polymer poly(NDI2OD-T2) (N2200) is one such material. While reasonably efficient organic solar cells can be fabricated with N2200 as the acceptor, it generally fails to contribute as much photocurrent from its absorption bands as the donor with which it is paired...

New strategies to synthesize nanometer-scale silicon dioxide (SiO2 ) patterns have drawn much attention in applications such as microelectronic and optoelectronic devices, membranes, and sensors, as we are approaching device dimensions shrinking below 10 nm. In this regard, sequential infiltration synthesis (SIS), a two-step gas-phase molecular assembly process that enables localized inorganic material growth in the targeted reactive domains of polymers, is an attractive process. In this work, we performed in situ Fourier transform infrared spectroscopy (FTIR) measurements during SiO2 SIS to investigate the reaction mechanism of trimethylaluminum (TMA) and tri(tert-pentoxy) silanol (TPS) precursors with polymers having ester functional groups (poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), polycaprolactone (PCL), and poly(t-butyl methacrylate) (PBMA)), for the purpose of growing patterned nanomaterials...

Transient absorption spectroscopy is a powerful technique to study the photoinduced phenomena in a wide range of states from solutions to solid film samples. It was designed and developed based on photoinduced absorption changes or that photoexcitation triggers a chain of reactions with intermediate states or reaction steps with presumably different absorption spectra. However, according to general electromagnetic theory, any change in the absorption properties of a medium is accompanied by a change in the refractive properties...

Light is a versatile tool to remotely activate molecules adsorbed on a surface, for example, to trigger their polymerization. Here, we explore the spatial distribution of light-induced chemical reactions on a Au(111) surface. Specifically, the covalent on-surface polymerization of an anthracene derivative in the submonolayer coverage range is studied. Using scanning tunneling microscopy and X-ray photoemission spectroscopy, we observe a substantial increase of the local molecular coverage with the sample illumination time at the center of the laser spot...

Sodium-ion batteries (NIBs) are promising systems for large-scale energy storage solutions; yet, further enhancements are required for their commercial viability. Improving the electrochemical performance of NIBs goes beyond the chemical description of the electrolyte and electrode materials as it requires a comprehensive understanding of the underlying mechanisms that govern the interface between electrodes and electrolytes. In particular, the decomposition reactions occurring at these interfaces lead to the formation of surface films...

Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu2 (Hbdea)2 Ni(CN)4 ] n ( 1 ) and [Cu2 (dmea)2 Ni(CN)4 ] n · n H2 O ( 2 ), were successfully self-assembled in water by reacting Cu(II) nitrate with H2 bdea ( N -butyldiethanolamine) and Hdmea ( N , N -dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN)4 ]2- . These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations...

Defects such as grain boundaries (GBs) are almost inevitable during the synthesis process of 2D materials. To take advantage of the fascinating properties of 2D materials, understanding the nature and impact of various GB structures on pristine 2D sheets is crucial. In this work, using an evolutionary algorithm search, we predict a wide variety of silicene GB structures with very different atomic structures compared with those found in graphene or hexagonal boron-nitride. Twenty-one GBs with the lowest energy were validated by density functional theory (DFT), a majority of which were previously unreported to our best knowledge...

The nonpolarizable force field for alkyl nitrates developed by Borodin et al. [ J. Phys. Chem. B , 2008 , 112 , 734-742] has been employed to calculate selected properties of crystalline and liquid erythritol tetranitrate (ETN). The set of partial charges proposed by Borodin for pentaerythritol tetranitrate (PETN) was used except for a small correction to the H atom charges to ensure charge neutrality owing to the absence of the neopentyl carbon in ETN. The force field was used to compute the isothermal compression curve, lattice parameters, heat capacity, thermal expansivity, single crystal elastic constants, and Gruneisen parameters of crystalline ETN...

Heat is an inexhaustible source of energy, and it can be exploited by thermoelectronics to produce electrical power or electrical responses. The search for a low-cost thermoelectric material that could achieve high efficiencies and can also be straightforwardly scalable has turned significant attention to the halide perovskite family. Here, we report the thermal voltage response of bismuth-based perovskite derivates and suggest a path to increase the electrical conductivity by applying chalcogenide doping. The films were produced by drop-casting or spin coating, and sulfur was introduced in the precursor solution using bismuth triethylxanthate...

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3 /LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67 Sr0.33 MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2 Nb3 O10 nanosheet-buffered 100 nm SiN x membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiN x membrane using fluorescence yield detection under electrocatalytic reaction conditions...

Spin-lattice relaxation measurements are used in 7 Li NMR studies of materials of potential use in solid-state Li-ion batteries as a probe of ion mobility on a fast (nanosecond to picosecond) time scale. The relaxation behavior is often analyzed by assuming exponential behavior or, equivalently, a single T 1 time constant. However, the spin-lattice relaxation of spin I = 3/2 nuclei, such as 7 Li, is in general biexponential; this is a fundamental property of I = 3/2 nuclei and unrelated to any compartmentalization within the solid...

Electrolyte species can significantly influence the electrocatalytic performance. In this work, we investigate the impact of alkali metal cations on the oxygen reduction reaction (ORR) on active Pt5 Gd and Pt5 Y polycrystalline electrodes. Due to the strain effects, Pt alloys exhibit a higher kinetic current density of ORR than pure Pt electrodes in acidic media. In alkaline solutions, the kinetic current density of ORR for Pt alloys decreases linearly with the decreasing hydration energy in the order of Li+ > Na+ > K+ > Rb+ > Cs+ , whereas Pt shows the opposite trend...

Solution-processable semiconductors with antiferromagnetic (AFM) order are attractive for future spintronics and information storage technology. Halide perovskites containing magnetic ions have emerged as multifunctional materials, demonstrating a cross-link between structural, optical, electrical, and magnetic properties. However, stable optoelectronic halide perovskites that are antiferromagnetic remain sparse, and the critical design rules to optimize magnetic coupling still must be developed. Here, we combine the complementary magnetometry and electron-spin-resonance experiments, together with first-principles calculations to study the antiferromagnetic coupling in stable Cs2 (Ag:Na)FeCl6 bulk semiconductor alloys grown by the hydrothermal method...

Environmentally persistent free radicals (EPFRs), a group of emerging pollutants, have significantly longer lifetimes than typical free radicals. EPFRs form by the adsorption of organic precursors on a transition metal oxide (TMO) surface involving electron charge transfer between the organic and TMO. In this paper, dihalogenated benzenes were incorporated to study the role of electronegativity in the electron transfer process to obtain a fundamental knowledge of EPFR formation mechanism on ZnO. Upon chemisorption on ZnO nanoparticles at 250 °C, electron paramagnetic resonance (EPR) confirms the formation of oxygen adjacent carbon-centered organic free radicals with concentrations between 1016 and 1017 spins/g...