Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO2(101)

Petrik, Nikolay G.; Wang, Yang; Wen, Bo; Wu, Yiqing; Ma, Runze; Dahal, Arjun; Gao, Feng; Rousseau, Roger; Wang, Yong; Kimmel, Greg A.; Selloni, Annabella; Dohnálek, Zdenek

doi:10.1021/acs.jpcc.1c00571

Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO₂(101)

Journal Article · Mon Apr 05 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c00571· OSTI ID:1774046

^[1]; Wang, Yang ^[2]; Wen, Bo ^[3]; Wu, Yiqing ^[2]; Ma, Runze ^[2]; ^[4]; ^[2]; ^[2]; ^[2]; ^[2]; ^[5]; ^[6]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Princeton University
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Princeton Univ., NJ (United States); Washington State Univ., Pullman, WA (United States); Henan Univ., Kaifeng (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of South Alabama, Mobile, AL (United States)
Princeton Univ., NJ (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Understanding thermochemical transformations of formic acid (FA) on metal oxide surfaces is important for many catalytical reactions. Here we study thermally induced reactions of FA on a single-crystalline and nanocrystalline anatase TiO₂(101). We employ a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) to follow the FA surface intermediates and reaction products above room temperature. We find that the primary reaction products desorbing at about 300, 480, and 515 K are molecular water, carbon monoxide, and formaldehyde, respectively. Bidentate (BD) formate and bridging hydroxyl (HO_b) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (V_O) are also likely participants despite their low stability at the surface. In conclusion, the parallel studies on single crystals and faceted TiO₂(101) nanoparticles reveal the spectroscopic commonalities of surface species and of the thermal conversion of molecular and deprotonated forms of FA.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL); Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; SC0007347

OSTI ID:: 1774046

Alternate ID(s):: OSTI ID: 1787859

Report Number(s):: PNNL-SA--159116

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 14 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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