In situ real-time environmental high resolution electron microscopy (EHREM) under controlled reaction environments permits direct atomic resolution imaging of dynamic surface and sub-surface microstructures of reacting catalysts. Using the EHREM and complementary microscopy methods, we have investigated selective hydrogenation reaction mechanisms over novel xerogel catalysts of ruthenium and Ru with Co and Au promoters on titania supports, and report an alternative heterogeneous catalytic process for the hydrogenation of adiponitrile (ADN) in the manufacture of Nylon 6,6. The direct EHREM observations are supported by ultra-high resolution low voltage scanning electron microscope (SEM) of spatial distributions of the highly dispersed nanometer-size catalyst particles and parallel chemical studies. The results demonstrate the important role of in situ EHREM in the design of heterogeneous catalytic hydrogenation processes on the nanoscale.