X-ray studies bridge the molecular and macro length scales during the emergence of CoO assemblies.

The key to fabricating complex, hierarchical materials is the control of chemical reactions at various length scales. To this end, the classical model of nucleation and growth fails to provide sufficient information. Here, we illustrate how modern X-ray spectroscopic and scattering in situ studies bridge the molecular- and macro- length scales for assemblies of polyhedrally shaped CoO nanocrystals. Utilizing high energy-resolution fluorescence-detected X-ray absorption spectroscopy, we directly access the molecular level of the nanomaterial synthesis. We reveal that initially Co(acac)3 rapidly reduces to square-planar Co(acac)2 and coordinates to two solvent molecules. Combining atomic pair distribution functions and small-angle X-ray scattering we observe that, unlike a classical nucleation and growth mechanism, nuclei as small as 2 nm assemble into superstructures of 20 nm. The individual nanoparticles and assemblies continue growing at a similar pace. The final spherical assemblies are smaller than 100 nm, while the nanoparticles reach a size of 6 nm and adopt various polyhedral, edgy shapes. Our work thus provides a comprehensive perspective on the emergence of nano-assemblies in solution.

Low-Temperature Carbon Dioxide Gas Sensor Based on Yolk-Shell Ceria Nanospheres.

Monitoring carbon dioxide (CO2) levels is extremely important in a wide range of applications. Although metal oxide-based chemoresistive sensors have emerged as a promising approach for CO2 detection, the development of efficient CO2 sensors at low temperature remains a challenge. Herein, we report a low-temperature hollow nanostructured CeO2-based sensor for CO2 detection. We monitor the changes in the electrical resistance after CO2 pulses in a relative humidity of 70% and show the high performance of the sensor at 100 °C. The yolk-shell nanospheres have not only 2 times higher sensitivity but also significantly increased stability and reversibility, faster response times, and greater CO2 adsorption capacity than commercial ceria nanoparticles. The improvements in the CO2 sensing performance are attributed to hollow and porous structure of the yolk-shell nanoparticles, allowing for enhanced gas diffusion and high specific surface area. We present an easy strategy to enhance the electrical and sensing properties of metal oxides at a low operating temperature that is desirable for practical applications of CO2 sensors.