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

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

doi:10.1021/acs.jpcc.1c00571

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

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

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

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 (HOb) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (VO) are also likely participants despite their low stability at the surface. Furthermore, 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.

Original language	English
Pages (from-to)	7686-7700
Number of pages	15
Journal	Journal of Physical Chemistry C
Volume	125
Issue number	14
DOIs	https://doi.org/10.1021/acs.jpcc.1c00571
State	Published - Apr 15 2021
Externally published	Yes

Funding

N.G.P., Ya.W, Yi.W., R.M., A.D., F.G., R.R., Yo.W., G.A.K., and Z.D. were supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (CSGB), under FWP 47319. B.W. and A.S. acknowledge the support of DOE BES, CSGB Division, under Award DESC0007347. The experimental studies were performed in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. We also acknowledge computational resources from the TIGRESS high-performance computer center at Princeton University.

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title = "Conversion of Formic Acid on Single- And Nano-Crystalline Anatase TiO2(101)",

abstract = "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 (HOb) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (VO) are also likely participants despite their low stability at the surface. Furthermore, 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.",

author = "Petrik, {Nikolay G.} and Yang Wang and Bo Wen and Yiqing Wu and Runze Ma and Arjun Dahal and Feng Gao and Roger Rousseau and Yong Wang and Kimmel, {Greg A.} and Annabella Selloni and Zdenek Dohn{\'a}lek",

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AU - Petrik, Nikolay G.

AU - Wang, Yang

AU - Wen, Bo

AU - Wu, Yiqing

AU - Ma, Runze

AU - Dahal, Arjun

AU - Gao, Feng

AU - Rousseau, Roger

AU - Wang, Yong

AU - Kimmel, Greg A.

AU - Selloni, Annabella

AU - Dohnálek, Zdenek

PY - 2021/4/15

Y1 - 2021/4/15

N2 - 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 (HOb) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (VO) are also likely participants despite their low stability at the surface. Furthermore, 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.

AB - 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 (HOb) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (VO) are also likely participants despite their low stability at the surface. Furthermore, 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.

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

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