Modulating the dynamics of Brønsted acid sites on PtWOx inverse catalyst

Fu, Jiayi; Liu, Shizhong; Zheng, Weiqing; Huang, Renjing; Wang, Cong; Lawal, Ajibola; Alexopoulos, Konstantinos; Liu, Sibao; Wang, Yunzhu; Yu, Kewei; Boscoboinik, J. Anibal; Liu, Yuefeng; Liu, Xi; Frenkel, Anatoly I.; Abdelrahman, Omar A.; Gorte, Raymond J.; Caratzoulas, Stavros; Vlachos, Dionisios G.

doi:10.1038/s41929-022-00745-y

Modulating the dynamics of Brønsted acid sites on PtWOx inverse catalyst

Journal Article · Mon Feb 21 00:00:00 EST 2022 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-022-00745-y· OSTI ID:1855097

Fu, Jiayi ^[1]; Liu, Shizhong ^[1]; Zheng, Weiqing ^[1]; ^[2]; Wang, Cong ^[1]; ^[3]; Alexopoulos, Konstantinos ^[1]; ^[4]; Wang, Yunzhu ^[1]; Yu, Kewei ^[1]; ^[5]; ^[6]; ^[7]; ^[8]; ^[3]; Gorte, Raymond J. ^[2]; Caratzoulas, Stavros ^[1]; ^[1]

Univ. of Delaware, Newark, DE (United States)
Univ. of Delaware, Newark, DE (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
Univ. of Delaware, Newark, DE (United States); Univ. of Massachusetts, Amherst, MA (United States)
Tianjin Univ., Tianjin (China)
Univ. of Delaware, Newark, DE (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
University of Chinese Academy of Sciences, Dalian (China)
Shanghai Jiao Tong Univ. (China)
Univ. of Delaware, Newark, DE (United States); Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Here metal-metal oxide (M-MO) inverse catalysts are broadly applied. Brønsted acid sites on the oxide overlayers are often hypothesized to drive selective C-O bond activation. However, the Brønsted acid site nature and dynamics under working conditions remain poorly understood due to multiple materials functionalities. Here, we investigate the formation and the dynamics of Brønsted acid and redox sites on PtWO_x/C under working conditions. DFT-based thermodynamic calculations and microkinetic modeling reveal a complex interplay between Brønsted acid and redox sites and potentially fast catalyst dynamics at comparable time scales to the chemistry. Combining in situ characterization and probe chemistry, we demonstrate that the density of Brønsted acid sites on the PtWO_x/C inverse catalyst could be modulated by up to two orders of magnitude by altering the reaction parameters and by the chemistry itself. We elicit an order of magnitude increase in the acid-catalyzed dehydration average reaction rate by periodic hydrogen pulsing.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: Chinese Academy of Science Youth Innovation Promotion Association; LiaoNing Revitalization Talents Program; National Natural Science Foundation of China; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0001004; SC0012704

OSTI ID:: 1855097

Alternate ID(s):: OSTI ID: 1847151
OSTI ID: 1854228

Report Number(s):: BNL-222864-2022-JAAM

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 2 Vol. 5; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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