For decades, differentially pumped environmental transmission electron microscopy has been a powerful tool to study dynamic structural evolution of catalysts under a gaseous environment. With the advancement of micro-electromechanical system-based technologies, windowed gas cell became increasingly popular due to its ability to achieve high pressure and its compatibility to a wide range of microscopes with minimal modification. This enables a series of imaging and analytical technologies such as atomic resolution imaging, spectroscopy, and operando, revealing details that were unprecedented before. By reviewing some of the recent work, we demonstrate that the windowed gas cell has the unique ability to solve complicated catalysis problems. We also discuss what technical difficulties need to be addressed and provide an outlook for the future of in situ environmental transmission electron microscopy (TEM) technologies and their application to the field of catalysis development.

Natural aging reduces the cost of alloy manufacturing while saving input energy but takes too long to complete for most Al-Zn-Mg-Cu alloys. Research has proved that nano-treating can facilitate precipitation in heat-treatable alloys. In this study, nano-treated Al-6.0Zn-2.6Mg-xCu samples containing different Cu contents were fabricated to investigate the influence of nano-treating on natural aging. TiC nanoparticles were used for nano-treating. Three cooling conditions after solution treatment (water quenching, air cooling, and as-cast) were investigated to check their quench sensitivities. The study shows the alloy’s microstructure was modified by nano-treating, and the growth of dendritic arms was inhibited. Compared to the control samples, nano-treating also increased both the microhardness and tensile strength of the alloy after natural aging. Out of the three different solution treatments, the air-cooled samples presented the highest UTS and microhardness values. The precipitation process was sped up by nano-treating by approximately 50%, and a higher volume fraction of GPII zones were formed in the nano-treated samples. HRTEM results also confirm the formation of more GPI and GPII zones in a nano-treated samples. With the help of natural aging, the Al-6.0Zn-2.6Mg-0.5Cu alloy reached a UTS of 455.7 ± 40.2 MPa and elongation of 4.52 ± 1.34% which makes it a great candidate for a naturally aged Al-Zn-Mg-Cu alloy.

Compositionally complex oxides (CCOs) are an emerging class of materials encompassing high entropy and entropy stabilized oxides (HEOs, ESOs). These promising advanced materials leverage tunable chemical bond structure, lattice distortion, and chemical disorder for unprecedented properties. Grain boundary (GB) and point defect segregation to GBs is relatively understudied in CCOs even though they can govern macroscopic material properties. For example, GB segregation can govern local chemical (dis)order and point defect distribution, playing a critical role in electrochemical reaction kinetics, and charge and mass transport in solid electrolytes. However, compared with conventional oxides, GBs in multi-cation CCO systems are expected to exhibit more complex segregation phenomena and thus prove more difficult to tune through GB design strategies. Here, GB segregation was studied in a model perovskite CCO LaFe0.7Ni0.1Co0.1Cu0.05Pd0.05O3-x textured thin film by (sub-)atomic-resolution scanning transmission electron microscopy imaging and spectroscopy. It is found that GB segregation is correlated with cation reducibility—predicted by an Ellingham diagram—as Pd and Cu segregate to GBs rich in oxygen vacancies (𝑉 𝑂 ∙∙). Furthermore, Pd and Cu segregation is highly sensitive to the concentration and spatial distribution of 𝑉 𝑂 ∙∙ along the GB plane, as well as fluctuations in atomic structure and elastic strain induced by GB local disorder, such as dislocations. This work offers a perspective of controlling segregation concentration of CCO cations to GBs by tuning reducibility of CCO cations and oxygen deficiency, which is expected to guide GB design in CCOs.

Electrocatalysts encapsulated by nanoscopic overlayers can catalyze redox reactions at the outer surface of the overlayer or at the buried interface between the overlayer and the active catalyst, leading to complex behavior in the presence of two competing electrochemical reactions. This study investigated oxide encapsulated electrocatalysts (OECs) comprised of iridium (Ir) thin films coated with an ultrathin (2-10 nm thick) silicon oxide (SiOx) or titanium oxide (TiOx) overlayer. The performance of SiOx|Ir and TiOx|Ir thin film electrodes towards the oxygen evolution reaction (OER) and Fe(II)/Fe(III) redox reactions were evaluated. An improvement in selectivity towards the OER was observed for all OECs. Overlayer properties, namely ionic and electronic conductivity, were assessed using a combination of electroanalytical methods and molecular dynamics simulations. SiOx and TiO¬x overlayers were found to be permeable to H2O and O2 such that the OER can occur at the MOx|Ir (M = Ti, Si) buried interface, which was further supported with molecular dynamics simulations. In contrast, Fe(II)/Fe(III) redox reactions occur to the same degree irrespective of whether electrocatalysts are bare, have TiOx overlayers with thicknesses less than 4 nm, or have SiOx overlayers with thicknesses less than 2 nm. This observation is attributed to facile electronic transport between the buried interface and outer surface of the overlayer, as measured with through-plane conductivity and ionic permeability measurements of wetted overlayer materials. These findings reveal the influence of oxide overlayer properties on the activity and selectivity of OECs and suggest opportunities to tune these properties for a wide range of electrochemical reactions.

The controlled integration of multiple components remains a significant challenge in the design of complex materials. Here, we present a strategy for synthesizing polyoxometalate (POM)-based coordination networks with up to three different cations in precisely defined positions. Our approach leverages a single-crystal-to-single-crystal transformation in which the spatial placement cations is governed by their availability at distinct stages of crystallization and transformation. Specifically, [ZP5W30O110](15−n)− (Z = Na+, K+, Ca2+, Ag+, Bi3+, Y3+, any Ln3+, Th4+) is coordinatively assembled with various bridging metal cations (Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Th4+). Using the encapsulated cation (Z) to label the POM, we track structural changes during the transformation, confirming the single-crystalline nature. Understanding this transformation pathway allows for rational control over the placement of different cations. These findings establish a versatile strategy for constructing multicomponent materials with exceptional compositional and spatial precision.