Changhong Cao

Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration

Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at −0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at −0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

Interfacial Shear Strength of Multilayer Graphene Oxide Films

Graphene oxide (GO) is considered as one of the most promising layered materials with tunable physical properties and applicability in many important engineering applications. In this work, the interfacial behavior of multilayer GO films was directly investigated via GO-to-GO friction force microscopy, and the interfacial shear strength (ISS) was measured to be 5.3 ± 3.2 MPa. Based on high resolution atomic force microscopy images and the available chemical data, targeted molecular dynamics simulations were performed to evaluate the influence of functional structure, topological defects, and interlayer registry on the shear response of the GO films. Theoretical values for shear strength ranging from 17 to 132 MPa were predicted for the different structures studied, providing upper bounds for the ISS. Computational results also revealed the atomic origins of the stochastic nature of friction measurements. Specifically, the wide scatter in experimental measurements was attributed to variations in functional structure and topological defects within the sliding volume. The findings of this study provide important insight for understanding the significant differences in strength between monolayer and bulk graphene oxide materials and can be useful for engineering topological structures with tunable mechanical properties.

Strengthening in Graphene Oxide Nanosheets: Bridging the Gap between Interplanar and Intraplanar Fracture

Graphene oxide (GO) is a layered material comprised of hierarchical features which possess vastly differing characteristic dimensions. GO nanosheets represent the critical hierarchical structure which bridges the length-scale of monolayer and bulk material architectures. In this study, the strength and fracture behavior of GO nanosheets were examined. Under uniaxial loading, the tensile strength of the nanosheets was measured to be as high as 12 ± 4 GPa, which approaches the intrinsic strength of monolayer GO and is orders of magnitude higher than that of bulk GO materials. During mechanical failure, brittle fracture was observed in a highly localized region through the cross-section of the nanosheets without interlayer pull-out. This transition in the failure behavior from interplanar fracture, common for bulk GO, to intraplanar fracture, which dominates failure in monolayer GO, is responsible for the high strength measured in the nanosheets. Molecular dynamics simulations indicate that the elastic release from the propagation of intraplanar cracks initiates global fracture due to interlayer load transmission through hydrogen bond networks within the gallery space of the GO nanosheets. Furthermore, the GO nanosheet strength and stiffness were found to be strongly correlated to the effective volume and thickness of the samples, respectively. These findings help to bridge the understanding of the mechanical behavior of hierarchical GO materials and will ultimately guide the application of this intermediate scale material.

Mechanical characterization of thin films using a MEMS device inside SEM

A MEMS device was developedfor mechanical characterization of 2D ultra-thin films. The device utilizes electrothermal actuators to apply uniaxial tension. The robust design makes the device capable of withstanding both dry and wet transfer of 2D ultra-thin film materials onto the suspended structures of the device. Fracture stress of thin graphene oxide (GO) films was measured.

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

Functionalized graphene multilayer is tougher than graphene. 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.

Mechanical stability of the cell nucleus: roles played by the cytoskeleton in nuclear deformation and strain recovery

ABSTRACT Extracellular forces transmitted through the cytoskeleton can deform the cell nucleus. Large nuclear deformations increase the risk of disrupting the integrity of the nuclear envelope and causing DNA damage. The mechanical stability of the nucleus defines its capability to maintain nuclear shape by minimizing nuclear deformation and allowing strain to be minimized when deformed. Understanding the deformation and recovery behavior of the nucleus requires characterization of nuclear viscoelastic properties. Here, we quantified the decoupled viscoelastic parameters of the cell membrane, cytoskeleton, and the nucleus. The results indicate that the cytoskeleton enhances nuclear mechanical stability by lowering the effective deformability of the nucleus while maintaining nuclear sensitivity to mechanical stimuli. Additionally, the cytoskeleton decreases the strain energy release rate of the nucleus and might thus prevent shape change-induced structural damage to chromatin. Summary: The viscoelastic parameters of the cell membrane, cytoskeleton and nucleus are decoupled, and the roles played by cytoskeleton in maintaining nuclear mechanical stability are deciphered.

Static and dynamic calibration of torsional spring constants of cantilevers

A method for calibrating the dynamic torsional spring constant of cantilevers by directly measuring the thermally driven motion of the cantilever with an interferometer is presented. Random errors in calibration were made negligible (<1%) by averaging over multiple measurements. The errors in accuracy of ±5% or ±10% for both of the cantilevers calibrated in this study were limited only by the accuracy of the laser Doppler vibrometer (LDV) used to measure thermal fluctuations. This is a significant improvement over commonly used methods that result in large and untraceable errors resulting from assumptions made about the cantilever geometry, material properties, and/or hydrodynamic physics of the surroundings. Subsequently, the static torsional spring constant is determined from its dynamic counterpart after careful LDV measurements of the torsional mode shape, backed by finite element analysis simulations. A meticulously calibrated cantilever is used in a friction force microscopy experiment that measures the friction difference and interfacial shear strength (ISS) between graphene and a silicon dioxide AFM probe. Accurate calibration can resolve discrepancies between different experimental methods, which have contributed to a large scatter in the reported friction and ISS values in the literature to date.

A MEMS device for fracture toughness measurement of 2D nano films under TEM imaging

This paper reports a transmission electron microscopy TEM-compatible MEMS device for the measurement of fracture toughness of 2D nano films. The MEMS device enables the creation of well-controlled electron-induced cracks in nano thin films, the measurement of film thickness, and tensile testing of films simultaneously all on chip. The device and techniques are applicable to the fracture toughness measurement of various types of nano films inside TEM.

Mechanical Characterization of Graphene

The emergence of monolayer carbon atom sheets, graphene, as a next generation advanced material, has potential applications in promising fields such as composite materials and energy storage. Graphene has exceptional mechanical properties, the most notable of which are ultrahigh strength and yield strain. Both experimental techniques and simulations have been performed for understanding mechanical properties of graphene such as, strength, yield strain, friction, and fracture behavior. This chapter summarizes the most recent findings on the mechanical characterization of graphene.