Journal ArticleDeoxydehydration of 1,4-anhydroerythritol over anatase TiO ₂ (101)-supported ReO _x and MoO _xXi, Yongjie; Lauterbach, Jochen; Pagan-Torres, Yomaira; Heyden, AndreasHeterogeneously catalyzed deoxydehydration (DODH) ordinarily occurs over relatively costly oxide supported ReO x sites and is an effective process for the removal of vicinal OH groups that are common in biomass-derived chemicals. Here, through first-principles calculations, we investigate the DODH of 1,4-anhydroerythritol over anatase TiO 2 (101)-supported ReO x and MoO x . The atomistic structures of ReO x and MoO x under typical reaction conditions were identified with constrained thermodynamics calculations as ReO 2 (2O)/6H–TiO 2 and MoO(2O)/3H–TiO 2 , respectively. The calculated energy profile and developed microkinetic reaction model suggest that both ReO 2 (2O)/6H–TiO 2 and MoO(2O)/3H–TiO 2 exhibit a relatively low DODH activity at 413 K. However, at higher temperatures such as 473 K, MoO(2O)/TiO 2 (101) was found to exhibit a reasonably high catalytic activity similar to ReO 2 (2O)/6H–TiO 2 , consistent with a recent experimental study. Mechanistically, the first O–H bond cleavage of 1,4-anhydroerythritol and the dihydrofuran extrusion were found to be the rate-controlling steps for the reaction over ReO 2 (2O)/6H–TiO 2 and MoO(2O)/3H–TiO 2 , respectively. Thus, this study clarifies the mechanism of the DODH over oxide-supported catalysts and provides meaningful insight into the design of low-cost DODH catalysts.2020-06-0810182220Catalysis Science & Technology10113731 to 37382044-4753https://doi.org/10.1039/d0cy00434k1632824National Science Foundation