Non-neglectable entropy effect on sintering of supported nanoparticles

Sintering refers to particle coalescence by heat, which has been known as a thermal phenomenon involving all aspects of natural science for centuries. It is particularly important in heterogeneous catalysis because normally sintering results in deactivation of the catalysts. In previous studies, the enthalpy contribution was considered to be dominant in sintering and the entropy effect is generally considered neglectable. However, we unambiguously demonstrate in this work that entropy could prevail over the enthalpy contribution to dominate the sintering behavior of supported nanoparticles (NPs) by designed experiments and improved theoretical framework. Using in situ Cs-corrected environmental scanning transmission electron microscopy and synchrotron-based ambient pressure X-ray photoelectron spectroscopy, we observe the unprecedent entropy-driven phenomenon that supported NPs reversibly redisperse upon heating and sinter upon cooling in three systems (Pd-CeO2, Cu-TiO2, Ag-TiO2). We quantitatively show that the configurational entropy of highly dispersed ad-atoms is large enough to reverse their sintering tendency at the elevated temperature. This work reshapes the basic understanding of sintering at the nanoscale and opens the door for various de-novo designs of thermodynamically stable nanocatalysts.