Center for Nanophase Materials Sciences

Defect sites play an essential role in ceria catalysis. In this study, ceria nanocrystals with well-defined surface planes have been synthesized and utilized for studying defect sites with both Raman spectroscopy and O(2) adsorption. Ceria nanorods ({110} + {100}), nanocubes ({100}), and nano-octahedra ({111}) are employed to analyze the quantity and quality of defect sites on different ceria surfaces. On oxidized surfaces, nanorods have the most abundant intrinsic defect sites, followed by nanocubes and nano-octahedra. When reduced, the induced defect sites are more clustered on nanorods than on nanocubes, although similar amounts (based on surface area) of such defect sites are produced on the two surfaces. Very few defect sites can be generated on the nano-octahedra due to the least reducibility. These differences can be rationalized by the crystallographic surface terminations of the ceria nanocrystals. The different defect sites on these nanocrystals lead to the adsorption of different surface dioxygen species. Superoxide on one-electron defect sites and peroxide on two-electron defect sites with different clustering degree are identified on the ceria nanocrystals depending on their morphology. Furthermore, the stability and reactivity of these oxygen species are also found to be surface-dependent, which is of significance for ceria-catalyzed oxidation reactions.

Herein we report on a general approach to delaminate multi-layered MXenes using an organic base to induce swelling that in turn weakens the bonds between the MX layers. Simple agitation or mild sonication of the swollen MXene in water resulted in the large-scale delamination of the MXene layers. The delamination method is demonstrated for vanadium carbide and titanium carbonitride MXenes.

Platinum group metal (PGM)-free catalysts for oxygen reduction reaction are essential for affordable fuel cells.

We report herein a hierarchically structured sulfur−carbon (S/C) nanocomposite material as the high surface-area cathode for rechargeable lithium batteries. A porous carbon with a uniform distribution of mesopores of 7.3 nm has been synthesized through a soft-template synthesis method. The potassium hydroxide activation of this mesoporous carbon results in a bimodal porous carbon with added microporosity of less than 2 nm to the existing mesopores without deterioration of the integrity of the original mesoporous carbon. Elemental sulfur has been loaded to the micropores through a solution infiltration method. The resulted S/C composites with various loading level of sulfur have a high surface areas and large internal porosities. These materials have been tested as novel cathodes for Li/S batteries. The results show that the cyclability and the utilization of sulfur in the Li/S batteries have been significantly improved. The large internal porosity and surface area of the micromesoporous carbon is essential for the high utilization of sulfur.

A systematic study of techniques for treating noncovalent interactions within the computationally efficient density functional theory (DFT) framework is presented through comparison to benchmark-quality evaluations of binding strength compiled for molecular complexes of diverse size and nature. In particular, the efficacy of functionals deliberately crafted to encompass long-range forces, a posteriori DFT+dispersion corrections (DFT-D2 and DFT-D3), and exchange-hole dipole moment (XDM) theory is assessed against a large collection (469 energy points) of reference interaction energies at the CCSD(T) level of theory extrapolated to the estimated complete basis set limit. The established S22 [revised in J. Chem. Phys. 132, 144104 (2010)] and JSCH test sets of minimum-energy structures, as well as collections of dispersion-bound (NBC10) and hydrogen-bonded (HBC6) dissociation curves and a pairwise decomposition of a protein-ligand reaction site (HSG), comprise the chemical systems for this work. From evaluations of accuracy, consistency, and efficiency for PBE-D, BP86-D, B97-D, PBE0-D, B3LYP-D, B970-D, M05-2X, M06-2X, ωB97X-D, B2PLYP-D, XYG3, and B3LYP-XDM methodologies, it is concluded that distinct, often contrasting, groups of these elicit the best performance within the accessible double-ζ or robust triple-ζ basis set regimes and among hydrogen-bonded or dispersion-dominated complexes. For overall results, M05-2X, B97-D3, and B970-D2 yield superior values in conjunction with aug-cc-pVDZ, for a mean absolute deviation of 0.41 - 0.49 kcal/mol, and B3LYP-D3, B97-D3, ωB97X-D, and B2PLYP-D3 dominate with aug-cc-pVTZ, affording, together with XYG3/6-311+G(3df,2p), a mean absolute deviation of 0.33 - 0.38 kcal/mol.

The controlled synthesis of materials by methods that permit their assembly into functional nanoscale structures lies at the crux of the emerging field of nanotechnology. Although only one of several materials families is of interest, carbon-based nanostructured materials continue to attract a disproportionate share of research effort, in part because of their wide-ranging properties. Additionally, developments of the past decade in the controlled synthesis of carbon nanotubes and nanofibers have opened additional possibilities for their use as functional elements in numerous applications. Vertically aligned carbon nanofibers (VACNFs) are a subclass of carbon nanostructured materials that can be produced with a high degree of control using catalytic plasma-enhanced chemical-vapor deposition (C-PECVD). Using C-PECVD the location, diameter, length, shape, chemical composition, and orientation can be controlled during VACNF synthesis. Here we review the CVD and PECVD systems, growth control mechanisms, catalyst preparation, resultant carbon nanostructures, and VACNF properties. This is followed by a review of many of the application areas for carbon nanotubes and nanofibers including electron field-emission sources, electrochemical probes, functionalized sensor elements, scanning probe microscopy tips, nanoelectromechanical systems (NEMS), hydrogen and charge storage, and catalyst support. We end by noting gaps in the understanding of VACNF growth mechanisms and the challenges remaining in the development of methods for an even more comprehensive control of the carbon nanofiber synthesis process.

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long-range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C(3)N(4)) and electronically active graphene. We find an inhomogeneous planar substrate (g-C(3)N(4)) promotes electron-rich and hole-rich regions, i.e., forming a well-defined electron-hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C(3)N(4) substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C(3)N(4) interface opens a 70 meV gap in g-C(3)N(4)-supported graphene, a feature that can potentially allow overcoming the graphene's band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C(3)N(4) is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C(3)N(4) monolayer, the hybrid graphene/g-C(3)N(4) complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

is a metal. This finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.

Platinum group metal-free (PGM-free) catalysts for the oxygen reduction reaction (ORR) with atomically dispersed FeN ₄ sites have emerged as a potential replacement for low-PGM catalysts in acidic polymer electrolyte fuel cells (PEFCs).

We describe plasmonic interactions in suspended gold bowtie nanoantenna leading to strong electromagnetic field (E) enhancements. Surface-enhanced Raman scattering (SERS) was used to demonstrate the performance of the nanoantenna. In addition to the well-known gap size dependence, up to 2 orders of magnitude additional enhancement is observed with elevated bowties. The overall behavior is described by a SERS enhancement factor exceeding 10(11) along with an anomalously weak power law dependence of E on the gap size in a range from 8 to 50 nm that is attributed to a plasmonic nanocavity effect occurring when the plasmonic interactions enter a strongly coupled regime.

The zigzag edge of a graphene nanoribbon possesses a unique electronic state that is near the Fermi level and localized at the edge carbon atoms. The authors investigate the chemical reactivity of these zigzag edge sites by examining their reaction energetics with common radicals from first principles. A "partial radical" concept for the edge carbon atoms is introduced to characterize their chemical reactivity, and the validity of this concept is verified by comparing the dissociation energies of edge-radical bonds with similar bonds in molecules. In addition, the uniqueness of the zigzag-edged graphene nanoribbon is further demonstrated by comparing it with other forms of sp2 carbons, including a graphene sheet, nanotubes, and an armchair-edged graphene nanoribbon.

HSAB theory predicts the design of air-stable, high-conduction sulfide based solid electrolytes.

Recent advances in scanning transmission electron and scanning probe microscopies have opened exciting opportunities in probing the materials structural parameters and various functional properties in real space with angstrom-level precision. This progress has been accompanied by an exponential increase in the size and quality of data sets produced by microscopic and spectroscopic experimental techniques. These developments necessitate adequate methods for extracting relevant physical and chemical information from the large data sets, for which a priori information on the structures of various atomic configurations and lattice defects is limited or absent. Here we demonstrate an application of deep neural networks to extract information from atomically resolved images including location of the atomic species and type of defects. We develop a "weakly supervised" approach that uses information on the coordinates of all atomic species in the image, extracted via a deep neural network, to identify a rich variety of defects that are not part of an initial training set. We further apply our approach to interpret complex atomic and defect transformation, including switching between different coordination of silicon dopants in graphene as a function of time, formation of peculiar silicon dimer with mixed 3-fold and 4-fold coordination, and the motion of molecular "rotor". This deep learning-based approach resembles logic of a human operator, but can be scaled leading to significant shift in the way of extracting and analyzing information from raw experimental data.

Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) reacts with humid air; the most favorable reaction pathway involves protonation of LLZO and formation of Li ₂ CO ₃ . The air exposure-induced contamination layer impacts the Li–LLZO interfacial resistance.

This review article gives insights on the current status and future perspectives of the lithium–sulfur battery technology.

Photocatalytic hydrogen evolution from water has received enormous attention due to its ability to address a number of global environmental and energy-related issues. Here, we synthesize 2D/2D Ti3C2/g-C3N4 composites by electrostatic self-assembly technique and demonstrate their use as photocatalysts for hydrogen evolution under visible light irradiation. The optimized Ti3C2/g-C3N4 composite exhibited a 10 times higher photocatalytic hydrogen evolution performance (72.3 μmol h-1 gcat-1) than that of pristine g-C3N4 (7.1 μmol h-1 gcat-1). Such enhanced photocatalytic performance was due to the formation of 2D/2D heterojunctions in the Ti3C2/g-C3N4 composites. The intimate contact between the monolayer Ti3C2 and g-C3N4 nanosheets promotes the separation of photogenerated charge carriers at the Ti3C2/g-C3N4 interface. Furthermore, the ultrahigh conductivity of Ti3C2 and the Schottky junction formed between g-C3N4/MXene interfaces facilitate the photoinduced electron transfer and suppress the recombination with photogenerated holes. This work demonstrates that the 2D/2D Ti3C2/g-C3N4 composites are promising photocatalysts thanks to the ultrathin MXenes as efficient co-catalysts for photocatalytic hydrogen production.

An infrared study has been conducted on CO 2 sorption into nanoporous CO 2 “molecular basket” sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75 °C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO 2 sorption capacity at higher temperatures. CO 2 sorption/desorption behavior studied by in situ transmission FTIR showed that CO 2 is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm −1 with CO 2 flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO 2 species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO 2 exposure time and with raising CO 2 sorption temperature. By comparison of the CO 2 sorption rate at 25 and 75 °C in terms of differential IR intensities, it was found that CO 2 sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO 2 is reversible at 75 °C. Comparative IR examination of the CO 2 sorption/desorption spectra on dry and prewetted PEI/SBA-15 sorbent revealed that presorbed water does not significantly affect the CO 2 −amine interaction patterns.

A TiNb ₂ O ₇ material with a nanoporous structure was prepared by a facile approach and can be used as an anode with excellent rate and cycling performance for long-life stationary lithium-ion batteries.

Ferroelectric materials have remained one of the major focal points of condensed matter physics and materials science for over 50 years. In the last 20 years, the development of voltage-modulated scanning probe microscopy techniques, exemplified by Piezoresponse force microscopy (PFM) and associated time- and voltage spectroscopies, opened a pathway to explore these materials on a single-digit nanometer level. Consequently, domain structures and walls and polarization dynamics can now be imaged in real space. More generally, PFM has allowed studying electromechanical coupling in a broad variety of materials ranging from ionics to biological systems. It can also be anticipated that the recent Nobel prize [“The Nobel Prize in Chemistry 2016,” http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2016/ (Nobel Media, 2016)] in molecular electromechanical machines will result in rapid growth in interest in PFM as a method to probe their behavior on single device and device assembly levels. However, the broad introduction of PFM also resulted in a growing number of reports on the nearly ubiquitous presence of ferroelectric-like phenomena including remnant polar states and electromechanical hysteresis loops in materials which are non-ferroelectric in the bulk or in cases where size effects are expected to suppress ferroelectricity. While in certain cases plausible physical mechanisms can be suggested, there is remarkable similarity in observed behaviors, irrespective of the materials system. In this review, we summarize the basic principles of PFM, briefly discuss the features of ferroelectric surfaces salient to PFM imaging and spectroscopy, and summarize existing reports on ferroelectric-like responses in non-classical ferroelectric materials. We further discuss possible mechanisms behind observed behaviors and possible experimental strategies for their identification.

This work reports a new strategy toward the design of a new class of supported catalysts with intrinsic high-temperature stabilities through entropy maximization.