Coupled Raman and temperature-programmed desorption for simultaneous analysis of structure and desorbed species from powder catalysts

Catalyst structure and surface chemistry are often studied separately, making it challenging to establish the structure–performance relationship under real reaction conditions. To address this, we develop a coupled Raman spectrometer and mass spectrometer system to enable simultaneous Raman and temperature-programmed desorption (TPD) analysis of powder catalysts under gaseous environments (1 × 10−8 to 1 × 103 mbar) and at temperatures from 100 to 1000 K with a linear heating rate up to 10 K s−1. This system minimizes re-adsorption effects in TPD analysis to ensure accurate measurement of desorption activation energies (ΔEdes), and furthermore, catalyst structure can be directly correlated with surface adsorbates based on the coupled Raman–TPD characterizations. Studies on D2 activation on ZnO reveal the role of oxygen vacancies in stabilizing D2 adsorption. In addition, spatially resolved TPD and Raman analyses of ZnO and ZnO/ZrO2 samples highlight the enhanced adsorption capacity and stability of H species on ZnO overlayers when confined on ZrO2 support.