WGS Catalysis and In Situ Studies of CoO1–x, PtCon/Co3O4, and PtmCom′/CoO1–x Nanorod Catalysts

Abstract

Water-gas shift (WGS) reactions on Co3O4 nanorods and Co3O4 nanorods anchoring singly dispersed Pt atoms were explored through building correlation of catalytic performance to surface chemistry of catalysts during catalysis using X-ray absorption spectroscopy, ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and environmental TEM. The active phase of pure Co3O4 during WGS is nonstoichiometric cobalt monoxide with about 20% oxygen vacancies, CoO0.80. The apparent activation energy (Ea) in the temperature range of 180-240 °C is 91.0 ± 10.5 kJ mol(-1). Co3O4 nanorods anchoring Pt atoms (Pt/Co3O4) are active for WGS with a low Ea of 50.1 ± 5.0 kJ mol(-1) in the temperature range of 150-200 °C. The active surface of this catalyst is singly dispersed Pt1Co(n) nanoclusters anchored on Co3O4 (Pt1/Co3O4), evidenced by in situ studies of extended X-ray absorption fine structure spectroscopy. In the temperature range of 200-300 °C, catalytic in situ studies suggested the formation of Pt(m)Co(m') nanoclusters along with the reduction of Co3O4 substrate to CoO(1-x). The new catalyst, Pt(m)Co(m')/CoO(1-x) is active for WGS with a very low Ea of 24.8 ± 3.1 kJ mol(-1) in the temperature range of 300-350 °C. The high activity could result from a synergy of Pt(m)Co(m') nanoclusters and surface oxygen vacancies of CoO(1-x).