A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

Yizhen Chen; Rachita Rana; Tyler Sours; Fernando D. Vila; Shaohong Cao; Thomas Blum; Jiyun Hong; Adam S. Hoffman; Chia Yu Fang; Zhennan Huang; Chunyan Shang; Chuanhao Wang; Jie Zeng; Miaofang Chi; Coleman X. Kronawitter; Simon R. Bare; Bruce C. Gates; Ambarish R. Kulkarni

doi:10.1021/jacs.1c07116

A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

Yizhen Chen, Rachita Rana, Tyler Sours, Fernando D. Vila, Shaohong Cao, Thomas Blum, Jiyun Hong, Adam S. Hoffman, Chia Yu Fang, Zhennan Huang, Chunyan Shang, Chuanhao Wang, Jie Zeng, Miaofang Chi, Coleman X. Kronawitter, Simon R. Bare, Bruce C. Gates, Ambarish R. Kulkarni

electron Microscopy and Microanalysis

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

36 Scopus citations

Abstract

Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.

Original language	English
Pages (from-to)	20144-20156
Number of pages	13
Journal	Journal of the American Chemical Society
Volume	143
Issue number	48
DOIs	https://doi.org/10.1021/jacs.1c07116
State	Published - Dec 8 2021

Funding

Y.C. and B.C.G. were supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) (Grant No. DE-FG02-04ER15513) and other DOE-supported institutions: Stanford Synchrotron Radiation Lightsource (SSRL) of SLAC National Accelerator Laboratory, supported by BES under Contract No. DE-AC02-76SF00515; Co-ACCESS, supported by the BES Chemical Sciences, Geosciences, and Biosciences Division. C.X.K. and A.R.K. were supported by DOE BES grant DE-SC0020320. Y.C. gratefully acknowledges the China Scholarship Council (CSC. No. 201806340062) for financial support. R.R. acknowledges support from the DOE (DE-SC0020320) for DFT calculations and SLAC for EXAFS analysis. T.S. was supported by start-up funds provided by the University of California, Davis, College of Engineering. Z.H. was supported by the DOE BES, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program. Electron microscopy was performed at Oak Ridge National Laboratory’s (ORNL) Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility (T.B., S.C., M.C.). The DFT calculations were performed using resources of the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract No. DE-AC02-05CH11231. Nudged elastic band calculations were done with support of the Extreme Science and Engineering Discovery Environment (XSEDE), supported by the National Science Foundation (Grant No. ACI-1548562). We thank Prof. Phillip Christopher (University of California, Santa Barbara) for providing data related to the Pt/TiO catalyst. 2

Access to Document

10.1021/jacs.1c07116

Cite this

Chen, Y., Rana, R., Sours, T., Vila, F. D., Cao, S., Blum, T., Hong, J., Hoffman, A. S., Fang, C. Y., Huang, Z., Shang, C., Wang, C., Zeng, J., Chi, M., Kronawitter, C. X., Bare, S. R., Gates, B. C., & Kulkarni, A. R. (2021). A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts. Journal of the American Chemical Society, 143(48), 20144-20156. https://doi.org/10.1021/jacs.1c07116

@article{a3f29a309a67453a9241f9fad81cfc7d,

title = "A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts",

abstract = "Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.",

author = "Yizhen Chen and Rachita Rana and Tyler Sours and Vila, {Fernando D.} and Shaohong Cao and Thomas Blum and Jiyun Hong and Hoffman, {Adam S.} and Fang, {Chia Yu} and Zhennan Huang and Chunyan Shang and Chuanhao Wang and Jie Zeng and Miaofang Chi and Kronawitter, {Coleman X.} and Bare, {Simon R.} and Gates, {Bruce C.} and Kulkarni, {Ambarish R.}",

year = "2021",

month = dec,

day = "8",

doi = "10.1021/jacs.1c07116",

language = "English",

volume = "143",

pages = "20144--20156",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "48",

}

Chen, Y, Rana, R, Sours, T, Vila, FD, Cao, S, Blum, T, Hong, J, Hoffman, AS, Fang, CY, Huang, Z, Shang, C, Wang, C, Zeng, J, Chi, M, Kronawitter, CX, Bare, SR, Gates, BC & Kulkarni, AR 2021, 'A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts', Journal of the American Chemical Society, vol. 143, no. 48, pp. 20144-20156. https://doi.org/10.1021/jacs.1c07116

TY - JOUR

T1 - A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

AU - Chen, Yizhen

AU - Rana, Rachita

AU - Sours, Tyler

AU - Vila, Fernando D.

AU - Cao, Shaohong

AU - Blum, Thomas

AU - Hong, Jiyun

AU - Hoffman, Adam S.

AU - Fang, Chia Yu

AU - Huang, Zhennan

AU - Shang, Chunyan

AU - Wang, Chuanhao

AU - Zeng, Jie

AU - Chi, Miaofang

AU - Kronawitter, Coleman X.

AU - Bare, Simon R.

AU - Gates, Bruce C.

AU - Kulkarni, Ambarish R.

PY - 2021/12/8

Y1 - 2021/12/8

N2 - Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.

AB - Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.

UR - http://www.scopus.com/inward/record.url?scp=85120327213&partnerID=8YFLogxK

U2 - 10.1021/jacs.1c07116

DO - 10.1021/jacs.1c07116

M3 - Article

C2 - 34806881

AN - SCOPUS:85120327213

SN - 0002-7863

VL - 143

SP - 20144

EP - 20156

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 48

ER -

A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this