In situ TEM tensile testing of carbon-linked graphene oxide nanosheets using a MEMS device.

This paper reports in situ transmission electron microscopy (TEM) tensile testing of carbon-linked graphene oxide nanosheets using a monolithic TEM compatible microelectromechanical system device. The set-up allows direct on-chip nanosheet thickness mapping, high resolution electron beam linking of a pre-fractured nanosheet, and mechanical tensile testing of the nanosheet. This technique enables simultaneous mechanical and high energy electron beam characterization of 2D nanomaterials.

Microstructure-Dependent Thermal Stability of Super-Tetragonal Nanocomposite Films through In Situ TEM/EELS Study.

Smart microstructure design in nanocomposite films allows us to tailor physical properties such as ferroelectricity and thermal stability to broaden applications of next-generation electronic devices. Here, we study the thermal stability of self-assembled PbTiO3 (PTO)/PbO nanocomposite films with nano-spherical and nanocolumnar microstructures by utilizing an environmental transmission electron microscopy (TEM) combined with electron energy loss spectroscopy (EELS). The real-time study reveals that the microstructure-dependent interphase strain has an effect on the stabilization of the tetragonal phase. Compared to the nano-spherical configuration, the nanocomposite film with the nanocolumnar microstructure can maintain the giant tetragonality of ∼1.20 up to 450 °C, and the tetragonal phase is predicted to be stable at elevated temperatures > 600 °C. Moreover, the temperature-dependent EELS further demonstrates the sensitivity of the chemical bonding of Pb and Ti with O to the PTO lattice distortion, correlating the structural variation and electronic properties at different temperatures. Such in situ heating TEM study provides insights into the thermal stability of nanocomposites with different microstructures and facilitates the advancement of power electronics applications in harsh environments.

Heterostructure Engineering of a Reverse Water Gas Shift Photocatalyst.

To achieve substantial reductions in CO2 emissions, catalysts for the photoreduction of CO2 into value-added chemicals and fuels will most likely be at the heart of key renewable-energy technologies. Despite tremendous efforts, developing highly active and selective CO2 reduction photocatalysts remains a great challenge. Herein, a metal oxide heterostructure engineering strategy that enables the gas-phase, photocatalytic, heterogeneous hydrogenation of CO2 to CO with high performance metrics (i.e., the conversion rate of CO2 to CO reached as high as 1400 µmol g cat-1 h-1) is reported. The catalyst is comprised of indium oxide nanocrystals, In2O3- x (OH) y , nucleated and grown on the surface of niobium pentoxide (Nb2O5) nanorods. The heterostructure between In2O3- x (OH) y nanocrystals and the Nb2O5 nanorod support increases the concentration of oxygen vacancies and prolongs excited state (electron and hole) lifetimes. Together, these effects result in a dramatically improved photocatalytic performance compared to the isolated In2O3- x (OH) y material. The defect optimized heterostructure exhibits a 44-fold higher conversion rate than pristine In2O3- x (OH) y . It also exhibits selective conversion of CO2 to CO as well as long-term operational stability.

Nonlinear fracture toughness measurement and crack propagation resistance of functionalized graphene multilayers.

Despite promising applications of two-dimensional (2D) materials, one major concern is their propensity to fail in a brittle manner, which results in a low fracture toughness causing reliability issues in practical applications. We show that this limitation can be overcome by using functionalized graphene multilayers with fracture toughness (J integral) as high as ~39 J/m2, measured via a microelectromechanical systems-based in situ transmission electron microscopy technique coupled with nonlinear finite element fracture analysis. The measured fracture toughness of functionalized graphene multilayers is more than two times higher than graphene (~16 J/m2). A linear fracture analysis, similar to that previously applied to other 2D materials, was also conducted and found to be inaccurate due to the nonlinear nature of the stress-strain response of functionalized graphene multilayers. A crack arresting mechanism of functionalized graphene multilayers was experimentally observed and identified as the main contributing factor for the higher fracture toughness as compared to graphene. Molecular dynamics simulations revealed that the interactions among functionalized atoms in constituent layers and distinct fracture pathways in individual layers, due to a random distribution of functionalized carbon atoms in multilayers, restrict the growth of a preexisting crack. The results inspire potential strategies for overcoming the relatively low fracture toughness of 2D materials through chemical functionalization.

Role of graphene in enhancing the mechanical properties of TiO2/graphene heterostructures.

Graphene has been integrated in many heterogeneous structures in order to take advantage of its superior mechanical properties. However, the complex mechanical response of heterogeneous films incorporating graphene is not well understood. Here, we studied the mechanical behavior of atomic layer deposition (ALD) synthesized TiO2/graphene, as a representative building block of a typical composite, to understand the mechanical behavior of heterostructures using an experiment-computational approach. The inclusion of graphene was found to significantly enhance the Young's modulus of TiO2/graphene hetero-films for films below a critical thickness of 3 nm, beyond which the Young's modulus approaches that of pure TiO2 film. A rule-of-mixtures was found to reasonably estimate the modulus of the TiO2/graphene hetero-film. Experimentally, these hetero-films were observed to fail via brittle fracture. Complimentary density functional theory and finite element modeling demonstrates strong adhesion at the graphene TiO2 interface and that graphene serves as a reinforcement, providing the hetero-film with an ability to sustain significantly high stresses at the point of failure initiation. The results and methodology described herein can contribute to the rational design of strong and reliable ultrathin hetero-films for versatile applications.

Photothermal Catalyst Engineering: Hydrogenation of Gaseous CO2 with High Activity and Tailored Selectivity.

This study has designed and implemented a library of hetero-nanostructured catalysts, denoted as Pd@Nb2O5, comprised of size-controlled Pd nanocrystals interfaced with Nb2O5 nanorods. This study also demonstrates that the catalytic activity and selectivity of CO2 reduction to CO and CH4 products can be systematically tailored by varying the size of the Pd nanocrystals supported on the Nb2O5 nanorods. Using large Pd nanocrystals, this study achieves CO and CH4 production rates as high as 0.75 and 0.11 mol h-1 gPd-1, respectively. By contrast, using small Pd nanocrystals, a CO production rate surpassing 18.8 mol h-1 gPd-1 is observed with 99.5% CO selectivity. These performance metrics establish a new milestone in the champion league of catalytic nanomaterials that can enable solar-powered gas-phase heterogeneous CO2 reduction. The remarkable control over the catalytic performance of Pd@Nb2O5 is demonstrated to stem from a combination of photothermal, electronic and size effects, which is rationally tunable through nanochemistry.

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5.

The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat-1 h-1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2 to valuable chemicals and fuels.

Mechanical stability enhancement by pore size and connectivity control in colloidal crystals by layer-by-layer growth of oxide.

Control of the pore size and connectivity of micro-sphere colloidal crystal lattices has been achieved by a layer-by-layer growth of silica using atmospheric pressure room temperature chemical vapour deposition of silica, a method which largely increases the mechanical stability of the lattice without disrupting its long range order.

Photomethanation of Gaseous CO2 over Ru/Silicon Nanowire Catalysts with Visible and Near-Infrared Photons.

Gaseous CO2 is transformed photochemically and thermochemically in the presence of H2 to CH4 at millimole per hour per gram of catalyst conversion rates, using visible and near-infrared photons. The catalyst used to drive this reaction comprises black silicon nanowire supported ruthenium. These results represent a step towards engineering broadband solar fuels tandem photothermal reactors that enable a three-step process involving i) CO2 capture, ii) gaseous water splitting into H2, and iii) reduction of gaseous CO2 by H2.

Periodic mesoporous organosilicas containing interconnected [Si(CH2)]3 rings.

A periodic mesoporous organosilica composed of interconnected three-ring [Si(CH2)]3 units built of three SiO2(CH2)2 tetrahedral subunits is reported. It represents the archetype of a previously unknown class of nanocomposite materials in which two bridging organic groups are bound to each silicon atom. It can be obtained with powder and oriented film morphologies. The nanocomposite is self-assembled from the cyclic three-ring silsesquioxane [(EtO)2Si(CH2)]3 precursor and a surfactant mesophase to give a well-ordered mesoporous framework. Low dielectric constants and good mechanical stability of the films were measured, making this material interesting for microelectronic applications. Methylene group reactivity of the three-ring precursor provides entry to a family of nanocomposites, exemplified by the synthesis and self-assembly of [(EtO)2Si(CHR)][(EtO)2Si(CH2)]2 (where R indicates iodine, bromine, or an ethyl group).