In Situ TEM under Optical Excitation for Catalysis Research.

In situ characterization of materials in their operational state is a highly active field of research. Investigating the structure and response of materials under stimuli that simulate real working environments for technological applications can provide new insight and unique input to the synthesis and design of novel materials. Over recent decades, experimental setups that allow different stimuli to be applied to a sample inside an electron microscope have been devised, built, and commercialized. In this review, we focus on the in situ investigation of optically active materials using transmission electron microscopy. We illustrate two different approaches for exposing samples to light inside the microscope column, explaining the importance of different aspects of their mechanical construction and choice of light source and materials. We focus on the technical challenges of the setups and provide details of the construction, providing the reader with input on deciding which setup will be more useful for a specific experiment. The use of these setups is illustrated using examples from the literature of relevance to photocatalysis and nanoparticle synthesis.

In situ manipulation of the active Au-TiO2 interface with atomic precision during CO oxidation.

The interface between metal catalyst and support plays a critical role in heterogeneous catalysis. An epitaxial interface is generally considered to be rigid, and tuning its intrinsic microstructure with atomic precision during catalytic reactions is challenging. Using aberration-corrected environmental transmission electron microscopy, we studied the interface between gold (Au) and a titanium dioxide (TiO2) support. Direct atomic-scale observations showed an unexpected dependence of the atomic structure of the Au-TiO2 interface with the epitaxial rotation of gold nanoparticles on a TiO2 surface during carbon monoxide (CO) oxidation. Taking advantage of the reversible and controllable rotation, we achieved in situ manipulation of the active Au-TiO2 interface by changing gas and temperature. This result suggests that real-time design of the catalytic interface in operating conditions may be possible.

Visualizing H2O molecules reacting at TiO2 active sites with transmission electron microscopy.

Imaging a reaction taking place at the molecular level could provide direct information for understanding the catalytic reaction mechanism. We used in situ environmental transmission electron microscopy and a nanocrystalline anatase titanium dioxide (001) surface with (1 × 4) reconstruction as a catalyst, which provided highly ordered four-coordinated titanium "active rows" to realize real-time monitoring of water molecules dissociating and reacting on the catalyst surface. The twin-protrusion configuration of adsorbed water was observed. During the water-gas shift reaction, dynamic changes in these structures were visualized on these active rows at the molecular level.

Methods for Calibration of Specimen Temperature During In Situ Transmission Electron Microscopy Experiments.

One of the biggest challenges for in situ heating transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) is the ability to measure the local temperature of the specimen accurately. Despite technological improvements in the construction of TEM/STEM heating holders, the problem of being able to measure the real sample temperature is still the subject of considerable discussion. In this study, we review the present literature on methodologies for temperature calibration. We analyze calibration methods that require the use of a thermometric material in addition to the specimen under study, as well as methods that can be performed directly on the specimen of interest without the need for a previous calibration. Finally, an overview of the most important characteristics of all the treated techniques, including temperature ranges and uncertainties, is provided in order to provide an accessory database to consult before an in situ TEM/STEM temperature calibration experiment.

Growth kinetics of single-walled carbon nanotubes with a (2n, n) chirality selection.

The growth kinetics play key roles in determining the chirality distribution of the grown single-walled carbon nanotubes (SWCNTs). However, the lack of comprehensive understandings on the SWCNT's growth mechanism at the atomic scale greatly hinders SWCNT chirality-selective synthesis. Here, we establish a general model, where the dislocation theory is a specific case, to describe the etching agent-dependent growth kinetics of SWCNTs on solid catalyst particles. In particular, the growth kinetics of SWCNTs in the absence of etching agent is validated by both in situ environmental transmission electron microscopy and ex situ chemical vapor deposition growth of SWCNTs. On the basis of the new theory of SWCNT's growth kinetics, we successfully explained the selective growth of (2n, n) SWCNTs. This study provides another degree of freedom for SWCNT controlled synthesis and opens a new strategy to achieve chirality-selective synthesis of (2n, n) SWCNTs using solid catalysts.

Self-assembled nanofibrils from RGD-functionalized cellulose nanocrystals to improve the performance of PEI/DNA polyplexes.

Cellulose nanocrystals (CNCs) are promising bio-derived nanomaterials for the bottom-up fabrication of biomedical constructs. In this report, dicarboxylic acid-functionalized CNC (DCC) was functionalized with arginylglycylaspartic acid (RGD) tripeptide as a motif for improved cell adhesion and targeting. The product (DCC-RGD) self-assembled into a more elongated nanofibrillar structure through lateral and end-to-end association. When added into poly(ethylene imine) (PEI)/pDNA polyplex solution, nanocelluloses interacted electrostatically with positively charged polyplexes without affecting their integrity. The constructs were tested for their potentials as non-viral transfection reagents. Cell viability and transfection efficiency of fibroblast NIH3T3 cells were monitored as a function of CNC concentration where, in general, viability increased as the CNC concentration increased, and transfection efficiency could be optimized. Using wild-type MDCK and αV-knockout MDCK cells, the construct was able to provide targeted uptake of polyplexes. The findings have potential applications, for example, cell-selective in vitro or ex vivo transfection of autologous mesenchymal stem cells for cell therapy, or bottom-up design of future innovative biomaterials.

Rationally Designed PdAuCu Ternary Alloy Nanoparticles for Intrinsically Deactivation-Resistant Ultrafast Plasmonic Hydrogen Sensing.

Hydrogen sensors are a prerequisite for the implementation of a hydrogen economy due to the high flammability of hydrogen-air mixtures. They are to comply with the increasingly stringent requirements set by stakeholders, such as the automotive industry and manufacturers of hydrogen safety systems, where sensor deactivation is a severe but widely unaddressed problem. In response, we report intrinsically deactivation-resistant nanoplasmonic hydrogen sensors enabled by a rationally designed ternary PdAuCu alloy nanomaterial, which combines the identified best intrinsic attributes of the constituent binary Pd alloys. This way, we achieve extraordinary hydrogen sensing metrics in synthetic air and poisoning gas background, simulating real application conditions. Specifically, we find a detection limit in the low ppm range, hysteresis-free response over 5 orders of magnitude hydrogen pressure, subsecond response time at room temperature, long-term stability, and, as the key, excellent resistance to deactivating species like carbon monoxide, notably without application of any protective coatings. This constitutes an important step forward for optical hydrogen sensor technology, as it enables application under demanding conditions and provides a blueprint for further material and performance optimization by combining and concerting intrinsic material assets in multicomponent nanoparticles. In a wider context, our findings highlight the potential of rational materials design through alloying of multiple elements for gas sensor development, as well as the potential of engineered metal alloy nanoparticles in nanoplasmonics and catalysis.

Metal-polymer hybrid nanomaterials for plasmonic ultrafast hydrogen detection.

Hydrogen-air mixtures are highly flammable. Hydrogen sensors are therefore of paramount importance for timely leak detection during handling. However, existing solutions do not meet the stringent performance targets set by stakeholders, while deactivation due to poisoning, for example by carbon monoxide, is a widely unsolved problem. Here we present a plasmonic metal-polymer hybrid nanomaterial concept, where the polymer coating reduces the apparent activation energy for hydrogen transport into and out of the plasmonic nanoparticles, while deactivation resistance is provided via a tailored tandem polymer membrane. In concert with an optimized volume-to-surface ratio of the signal transducer uniquely offered by nanoparticles, this enables subsecond sensor response times. Simultaneously, hydrogen sorption hysteresis is suppressed, sensor limit of detection is enhanced, and sensor operation in demanding chemical environments is enabled, without signs of long-term deactivation. In a wider perspective, our work suggests strategies for next-generation optical gas sensors with functionalities optimized by hybrid material engineering.

2D Transition Metal Carbides (MXenes) for Carbon Capture.

Global warming caused by burning of fossil fuels is indisputably one of mankind's greatest challenges in the 21st century. To reduce the ever-increasing CO2 emissions released into the atmosphere, dry solid adsorbents with large surface-to-volume ratio such as carbonaceous materials, zeolites, and metal-organic frameworks have emerged as promising material candidates for capturing CO2 . However, challenges remain because of limited CO2 /N2 selectivity and long-term stability. The effective adsorption of CO2 gas (≈12 mol kg-1 ) on individual sheets of 2D transition metal carbides (referred to as MXenes) is reported here. It is shown that exposure to N2 gas results in no adsorption, consistent with first-principles calculations. The adsorption efficiency combined with the CO2 /N2 selectivity, together with a chemical and thermal stability, identifies the archetype Ti3 C2 MXene as a new material for carbon capture (CC) applications.

Direct In Situ TEM Visualization and Insight into the Facet-Dependent Sintering Behaviors of Gold on TiO2.

Preventing sintering of supported nanocatalysts is an important issue in nanocatalysis. A feasible way is to choose a suitable support. However, whether the metal-support interactions promote or prevent the sintering has not been fully identified. Now, completely different sintering behaviors of Au nanoparticles on distinct anatase TiO2 surfaces have been determined by in situ TEM. The full in situ sintering processes of Au nanoparticles were visualized on TiO2 (101) surface, which coupled the Ostwald ripening and particle migration coalescence. In contrast, no sintering of Au on TiO2 anatase (001) surface was observed under the same conditions. This facet-dependent sintering mechanism is fully explained by the density function theory calculations. This work not only offers direct evidence of the important role of supports in the sintering process, but also provides insightful information for the design of sintering-resistant nanocatalysts.

Accuracy of surface strain measurements from transmission electron microscopy images of nanoparticles.

Strain analysis from high-resolution transmission electron microscopy (HRTEM) images offers a convenient tool for measuring strain in materials at the atomic scale. In this paper we present a theoretical study of the precision and accuracy of surface strain measurements directly from aberration-corrected HRTEM images. We examine the influence of defocus, crystal tilt and noise, and find that absolute errors of at least 1-2% strain should be expected. The model structures include surface relaxations determined using molecular dynamics, and we show that this is important for correctly evaluating the errors introduced by image aberrations.

Grain boundary mediated hydriding phase transformations in individual polycrystalline metal nanoparticles.

Grain boundaries separate crystallites in solids and influence material properties, as widely documented for bulk materials. In nanomaterials, however, investigations of grain boundaries are very challenging and just beginning. Here, we report the systematic mapping of the role of grain boundaries in the hydrogenation phase transformation in individual Pd nanoparticles. Employing multichannel single-particle plasmonic nanospectroscopy, we observe large variation in particle-specific hydride-formation pressure, which is absent in hydride decomposition. Transmission Kikuchi diffraction suggests direct correlation between length and type of grain boundaries and hydride-formation pressure. This correlation is consistent with tensile lattice strain induced by hydrogen localized near grain boundaries as the dominant factor controlling the phase transition during hydrogen absorption. In contrast, such correlation is absent for hydride decomposition, suggesting a different phase-transition pathway. In a wider context, our experimental setup represents a powerful platform to unravel microstructure-function correlations at the individual-nanoparticle level.

Direct observation of nanowire growth and decomposition.

Fundamental concepts of the crystal formation suggest that the growth and decomposition are determined by simultaneous embedding and removal of the atoms. Apparently, by changing the crystal formation conditions one can switch the regimes from the growth to decomposition. To the best of our knowledge, so far this has been only postulated, but never observed at the atomic level. By means of in situ environmental transmission electron microscopy we monitored and examined the atomic layer transformation at the conditions of the crystal growth and its decomposition using CuO nanowires selected as a model object. The atomic layer growth/decomposition was studied by varying an O2 partial pressure. Three distinct regimes of the atomic layer evolution were experimentally observed: growth, transition and decomposition. The transition regime, at which atomic layer growth/decomposition switch takes place, is characterised by random nucleation of the atomic layers on the growing {111} surface. The decomposition starts on the side of the nanowire by removing the atomic layers without altering the overall crystal structure, which besides the fundamental importance offers new possibilities for the nanowire manipulation. Understanding of the crystal growth kinetics and nucleation at the atomic level is essential for the precise control of 1D crystal formation.

Growth Termination and Multiple Nucleation of Single-Wall Carbon Nanotubes Evidenced by in Situ Transmission Electron Microscopy.

In order to controllably grow single-wall carbon nanotubes (SWCNTs), a better understanding of the growth processes and how they are influenced by external parameters such as catalyst and gaseous environment is required. Here, we present direct evidence of growth termination of individual SWCNTs and successive growth of additional SWCNTs on Co catalyst particles supported on MgO by means of environmental transmission electron microscopy. Such in situ observations reveal the plethora of solid carbon formations at the local scale while it is happening and thereby elucidate the multitude of configurations resulting from identical external synthesis conditions, which should be considered in the quest for controlled SWCNT growth. Using CO and a mixture of CO and H2 as carbon sources, we show that the growth of SWCNTs terminates with a reduced tube-catalyst adhesion strength. Two main reasons for the cessation are proposed: insufficient active carbon species and a certain amount of stress exerted at the tube-catalyst interface. Interestingly, it was observed that catalyst particles stayed active in terms of nucleating additional solid carbon structures after growth termination of the first SWCNT. These observations elucidate the importance of an in-depth understanding of the role of catalysts and carbon sources in the continued growth of SWCNTs. Furthermore, it serves as a guide for further control of carbon nanostructure synthesis via catalyst engineering and synthesis optimization.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Correction to: Accuracy of surface strain measurements from transmission electron microscopy images of nanoparticles.

[This corrects the article DOI: 10.1186/s40679-017-0047-0.].

Current status and future directions for in situ transmission electron microscopy.

This review article discusses the current and future possibilities for the application of in situ transmission electron microscopy to reveal synthesis pathways and functional mechanisms in complex and nanoscale materials. The findings of a group of scientists, representing academia, government labs and private sector entities (predominantly commercial vendors) during a workshop, held at the Center for Nanoscale Science and Technology- National Institute of Science and Technology (CNST-NIST), are discussed. We provide a comprehensive review of the scientific needs and future instrument and technique developments required to meet them.

In Situ Ptychography of Heterogeneous Catalysts using Hard X-Rays: High Resolution Imaging at Ambient Pressure and Elevated Temperature.

A new closed cell is presented for in situ X-ray ptychography which allows studies under gas flow and at elevated temperature. In order to gain complementary information by transmission and scanning electron microscopy, the cell makes use of a Protochips E-chipTM which contains a small, thin electron transparent window and allows heating. Two gold-based systems, 50 nm gold particles and nanoporous gold as a relevant catalyst sample, were used for studying the feasibility of the cell. Measurements showing a resolution around 40 nm have been achieved under a flow of synthetic air and during heating up to temperatures of 933 K. An elevated temperature exhibited little influence on image quality and resolution. With this study, the potential of in situ hard X-ray ptychography for investigating annealing processes of real catalyst samples is demonstrated. Furthermore, the possibility to use the same sample holder for ex situ electron microscopy before and after the in situ study underlines the unique possibilities available with this combination of electron microscopy and X-ray microscopy on the same sample.

Bottom-Up Nanofabrication of Supported Noble Metal Alloy Nanoparticle Arrays for Plasmonics.

Mixing different elements at the nanoscale to obtain alloy nanostructures with fine-tuned physical and chemical properties offers appealing opportunities for nanotechnology and nanoscience. However, despite widespread successful application of alloy nanoparticles made by colloidal synthesis in heterogeneous catalysis, nanoalloy systems have been used very rarely in solid-state devices and nanoplasmonics-related applications. One reason is that such applications require integration in arrays on a surface with compelling demands on nanoparticle arrangement, uniformity in surface coverage, and optimization of the surface density. These cannot be fulfilled even using state-of-the-art self-assembly strategies of colloids. As a solution, we present here a generic bottom-up nanolithography-compatible fabrication approach for large-area arrays of alloy nanoparticles on surfaces. To illustrate the concept, we focus on Au-based binary and ternary alloy systems with Ag, Cu, and Pd, due to their high relevance for nanoplasmonics and complete miscibility, and characterize their optical properties. Moreover, as an example for the relevance of the obtained materials for integration in devices, we demonstrate the superior and hysteresis-free plasmonic hydrogen-sensing performance of the AuPd alloy nanoparticle system.

Stable amorphous georgeite as a precursor to a high-activity catalyst.

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable--and hence little known and largely ignored--georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions--a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.