Understanding Methanol Coupling on SrTiO3 from First Principles

Huang, Runhong; Fung, Victor; Zhang, Yafen; Mullins, David R.; Wu, Zili; Jiang, De-en

doi:10.1021/acs.jpcc.8b00273

Title: Understanding Methanol Coupling on SrTiO₃ from First Principles

Abstract

Perovskites are interesting materials for catalysis due to their great tunability. However, the correlation of many reaction processes to the termination of a perovskite surface is still unclear. In this paper, we use the methanol coupling reaction on the SrTiO₃(100) surface as a probe reaction to investigate direct C–C coupling from a computational perspective. We use density functional theory to assess methanol adsorption, C–H activation, and direct C–C coupling reactions on the SrTiO₃(100) surface of different terminations. We find that, although methanol molecules dissociatively adsorb on both A and B terminations with similar strength, the dehydrogenation and C–C coupling reactions have significantly lower activation energies on the B termination than on the A termination. The predicted formation of methoxy and acetate on the SrTiO₃(100) B termination can well explain the ambient-pressure XPS data of methanol on the single-crystal SrTiO₃(100) surface at 250 °C. Finally, this work suggests that a choice of B termination of perovskites would be beneficial for the C–C coupling reaction of methanol.

Authors:

Huang, Runhong ^[1];

^[1]; Zhang, Yafen ^[2];

^[2];

^[3];

^[1]

Univ. of California, Riverside, CA (United States). Dept. of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division. Center for Nanophase Materials Sciences

Publication Date:: Mon Mar 19 00:00:00 EDT 2018

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1435220

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231; SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 13; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Huang, Runhong, Fung, Victor, Zhang, Yafen, Mullins, David R., Wu, Zili, and Jiang, De-en. Understanding Methanol Coupling on SrTiO3 from First Principles.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b00273.

Copy to clipboard


                    Huang, Runhong, Fung, Victor, Zhang, Yafen, Mullins, David R., Wu, Zili, & Jiang, De-en. Understanding Methanol Coupling on SrTiO3 from First Principles.  United States.  https://doi.org/10.1021/acs.jpcc.8b00273

Copy to clipboard


                    Huang, Runhong, Fung, Victor, Zhang, Yafen, Mullins, David R., Wu, Zili, and Jiang, De-en. Mon .  
"Understanding Methanol Coupling on SrTiO3 from First Principles".  United States.  https://doi.org/10.1021/acs.jpcc.8b00273.  https://www.osti.gov/servlets/purl/1435220.

Copy to clipboard


                    
@article{osti_1435220,

  title        = {Understanding Methanol Coupling on SrTiO3 from First Principles},

  author       = {Huang, Runhong and Fung, Victor and Zhang, Yafen and Mullins, David R. and Wu, Zili and Jiang, De-en},

  abstractNote = {Perovskites are interesting materials for catalysis due to their great tunability. However, the correlation of many reaction processes to the termination of a perovskite surface is still unclear. In this paper, we use the methanol coupling reaction on the SrTiO3(100) surface as a probe reaction to investigate direct C–C coupling from a computational perspective. We use density functional theory to assess methanol adsorption, C–H activation, and direct C–C coupling reactions on the SrTiO3(100) surface of different terminations. We find that, although methanol molecules dissociatively adsorb on both A and B terminations with similar strength, the dehydrogenation and C–C coupling reactions have significantly lower activation energies on the B termination than on the A termination. The predicted formation of methoxy and acetate on the SrTiO3(100) B termination can well explain the ambient-pressure XPS data of methanol on the single-crystal SrTiO3(100) surface at 250 °C. Finally, this work suggests that a choice of B termination of perovskites would be beneficial for the C–C coupling reaction of methanol.},

  doi          = {10.1021/acs.jpcc.8b00273},

  journal      = {Journal of Physical Chemistry. C},

  number       = 13,

  volume       = 122,

  place        = {United States},

  year         = {Mon Mar 19 00:00:00 EDT 2018},

  month        = {Mon Mar 19 00:00:00 EDT 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpcc.8b00273

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

Figures / Tables:

Figure 1: Atomistic models of the SrTiO₃(100) surface of A termination and B termination. Color code: Sr, green; Ti, cyan; O, red.

All figures and tables (8 total)

Save / Share:

Export Metadata

Save to My Library

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Adsorption and Reaction of Methanol on Stoichiometric and Defective SrTiO{sub 3}(100) Surfaces

Journal Article Wang, Li Q ; Ferris, Kim F ; Azad, Samina ; ... - Journal of Physical Chemistry B

The adsorption and reaction of methanol (CH{sub 3}OH) on stoichiometric (TiO{sub 2}-terminated) and reduced SrTiO{sub 3}(100) surfaces have been investigated using temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and first-principles density-functional calculations. Methanol adsorbs mostly nondissociatively on the stoichiometric SrTiO{sub 3}(100) surface that contains predominantly Ti{sup 4+} cations. Molecular desorption of methanol from the stoichiometric surface is observed at {approx}250 K whereas the multilayer is found to desorb at {approx}160 K. Theoretical calculations predict weak adsorption of methanol on TiO{sub 2}-terminated SrTiO{sub 3}(100) surfaces, in agreement with the experimental results. However, the reduced SrTiO{sub 3}(100) surface containing substantial amountsmore »« less
https://doi.org/10.1021/jp048338t
Highly Selective Methane to Methanol Conversion on Inverse SnO₂/Cu₂O/Cu(111) Catalysts: Unique Properties of SnO₂ Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Journal Article Huang, Erwei ; Rui, Ning ; Rosales, Rina ; ... - ACS Catalysis

Direct methane to methanol (CH₄ → CH₃OH) conversion in heterogeneous catalysis has been a long-standing challenge due to the difficulties in equalizing the activation of methane and protection of the methanol product at the same reaction conditions. Here, we report an inverse catalyst, consisting of small structures of SnO₂ (0.5-1 nm in size) dispersed on Cu₂O/Cu(111), for highly selective CH₃OH production from CH₄. This system was investigated by combining theoretical [density functional theory calculations (DFT), kinetic Monte Carlo simulations (KMC)] and experimental methods [scanning tunneling microscopy (STM), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)]. The DFT and AP-XPS studies showed that onmore »« less
https://doi.org/10.1021/acscatal.2c03060

Full Text Available
Interaction of HCOOH with stoichiometric and reduced SrTiO{sub 3}(100) surfaces

Journal Article Wang, Li-Qiong ; Ferris, K F ; Herman, G S ; ... - Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films

Interaction of formic acid with stoichiometric (TiO{sub 2}-terminated) and reduced SrTiO{sub 3}(100) surfaces has been investigated using temperature programmed desorption (TPD), and x-ray photoelectron spectroscopy (XPS). Formic acid was dissociated to form formate and a surface proton below 250 K on both stoichiometric and reduced SrTiO{sub 3}(100) surfaces. Formate was decomposed primarily through dehydration to produce CO and H{sub 2}O, instead of through dehydrogenation to produce CO{sub 2} and H{sub 2}, on both surfaces. Formaldehyde produced from decomposition of formate was also observed on both surfaces. On stoichiometric surfaces, formaldehyde was produced through bimolecular coupling of two formates on low-coordinationmore »« less
https://doi.org/10.1116/1.582442
Adsorption and Reaction of Acetaldehyde on Stoichiometric and Defective SrTiO{sub 3}(100) Surfaces

Journal Article Wang, Li Q ; Ferris, Kim F ; Azad, Samina ; ... - Journal of Physical Chemistry B

The adsorption and reaction of acetaldehyde (CH{sub 3}CHO), on stoichiometric (TiO{sub 2}-terminated) and reduced SrTiO{sub 3}(100) surfaces, have been investigated using temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Acetaldehyde adsorbs molecularly on the stoichiometric SrTiO{sub 3}(100) surface that contains predominantly Ti{sup 4+} cations. The Ti{sup 4+} sites on the stoichiometric SrTiO{sub 3}(100) surface are not sufficiently active for surface reactions such as aldol condensation, as opposed to the Ti{sup 4+} ions on the TiO{sub 2}(001) surface. However, decomposition and redox reactions of acetaldehyde occur in the presence of surface defects created by Ar{sup +} sputtering. The decomposition products followingmore »« less
https://doi.org/10.1021/jp030917v
Shape Effect Undermined by Surface Reconstruction: Ethanol Dehydrogenation over Shape-Controlled SrTiO₃ Nanocrystals

Journal Article Foo, Guo Shiou ; Hood, Zachary D. ; Wu, Zili - ACS Catalysis

For this research, to gain an in-depth understanding of the surface properties relevant for catalysis using ternary oxides, we report the acid–base pair reactivity of shape-controlled SrTiO₃ (STO) nanocrystals for the dehydrogenation of ethanol. Cubes, truncated cubes, dodecahedra, and etched cubes of STO with varying ratios of (001) and (110) crystal facets were synthesized using a hydrothermal method. Low-energy ion scattering (LEIS) analysis revealed that the (001) surface on cubes of STO is enriched with SrO due to surface reconstruction, resulting in a high ratio of strong base sites. Chemical treatment with dilute nitric acid to form etched cubes ofmore »« less
Cited by 48
https://doi.org/10.1021/acscatal.7b03341

Full Text Available

Similar Records

Title: Understanding Methanol Coupling on SrTiO3 from First Principles

Abstract

Citation Formats

Figures / Tables:

Title: Understanding Methanol Coupling on SrTiO₃ from First Principles