Catalytic nanomaterials play a major role in chemical conversions and energy transformations. Understanding how materials control and regulate surface reactions is a major objective for fundamental research on heterogeneous catalysts. In situ environmental transmission electron microscopy (ETEM) is a powerful technique for revealing the atomic structures of materials at elevated temperatures in the presence of reactive gases. This approach can allow the structure–reactivity relations underlying catalyst functionality to be investigated. Thus far, ETEM has been limited by the absence of in situ measurements of gas-phase catalytic products. To overcome this deficiency, operando TEM techniques are being developed that combine atomic characterization with the simultaneous measurement of catalytic products. This article provides a short review of the current status and major developments in the application of ETEM to gas-phase catalysis over the past 10 years.

The Ni/NiO core/shell structure is one of the most efficient co-catalysts for solar water splitting when coupled with suitable semiconducting oxides. It has been shown that pretreated Ni/NiO core/shell structures are more active than pure Ni metal, pure NiO or mixed dispersion of Ni metal and NiO nanoparticles. However, Ni/NiO core/shell structures on TiO2 are only able to generate H2 but not O2 in aqueous water. The nature of the hydrogen evolution reaction in these systems was investigated by correlating photochemical H2 production with atomic resolution structure determined with aberration corrected electron microscopy. It was found that the core/shell structure plays an important role for H2 generation but the system undergoes deactivation due to a loss of metallic Ni. During the H2 evolution reaction, the metal core initially formed partial voids which grew and eventually all the Ni diffused out of the core-shell into solution leaving an inactive hollow NiO void structure. The H2 evolution was generated by a photochemical reaction involving photocorrosion of Ni metal.

The morphology, microstructure, and composition of the submicron fraction of individual light-absorbing carbon (LAC) particles collected by research aircraft during the ACE-Asia (Asian Pacific Regional Aerosol Characterization Experiment) project above the Yellow Sea at altitudes of 120, 450 and 1500 m are investigated by transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). Two types of carbonaceous particles, small spherule soot with graphitic spherules and amorphous carbonaceous spheres (brown carbon), are found at all altitudes in high concentration. For soot particles, emphasis of the study is on the component subparticles (spherules). The nanoscopic structures of the small spherule soot show no significant difference at three altitudes although the size distribution of primary spherules showed that 70% of the total volume lies in the ranges 30–50, 50–85 and 30–50 nm, respectively. For the amorphous carbonaceous spheres, 70% of the total volume from three altitudes lies in the range 200–350, 160–470 and 150–320 nm, respectively. Within the size fraction studied (submicron, with most particles in the range 50 to 500 nm) the number concentration ratios of the amorphous carbonaceous spheres to primary spherules in soot at altitudes of 120, 450 and 1500 m are about 1, 1.5 and 10, respectively and their volume ratios are about 260, 50 and 1400. Lower relative concentrations of large spherule soot with intermediate graphitic structure were observed at 120 m. Also, low relative number concentrations of carbon cenospheres were observed at 120 and 1500 m. A key result of the study is that in vertically stratified outflow from East Asia, the character of LAC may have strong variance with altitude thus resulting in optical characteristics that vary with altitude. Also, apparent "aging" of LAC deduced from samples at multiple ground stations may instead reflect differences in the original carbon aerosols.