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Title: Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions

Abstract

We report the direct use of inorganometallic gold complexes formed in alkaline solutions as robust heterogeneous catalysts. Specifically, mononuclear gold complexes with the gold atom surrounded by a shell of Na cations through -O- linkages were prepared by dissolving Au(OH)3 in highly alkaline solutions of NaOH. The complexes remain intact upon impregnation onto supports or after drying in air to a crystalline powder. Supported catalysts containing exclusively atomic gold at loadings up to 1.2 wt.% Au were prepared. Either in supported or unsupported form, the mononuclear gold-centered oxo-clusters catalyze the selective methanol dehydrogenation reaction to methyl formate (MF) and hydrogen; a reaction of industrial interest as well as the key step in methanol steam reforming. The [Au1-Ox]- center was identified as the active catalytic site by experimental characterization and density functional theory studies. The methanol dehydrogenation reaction mechanism proceeds via the self-coupling of methanol to MF. No oxygen supply is necessary. Hence, hydrogen rather than water is produced at 2:1 (stoichiometric) molar ratio to MF. The dried crystalline powder of the solution was used as an unsupported catalyst, showing the same chemistry as the supported clusters. Ab initio molecular dynamics (AIMD) simulations of methanol self-coupling on the mononuclear gold clustersmore » revealed the formation of formate spectators on the clusters under reaction conditions, also corroborated by in situ DRIFTS. The inclusion of these spectators proved crucial towards the accurate description of the energetics of self-coupling of methanol on these clusters, thus unravelling the nature of the active site. Catalyst stability up to 250-300 oC in reaction conditions is demonstrated.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [1];  [2];  [3];  [1];  [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [2]; ORCiD logo [1]
  1. Tufts Univ., Medford, MA (United States)
  2. Univ. of Wisconsin, Madison, WI (United States)
  3. Stony Brook Univ., NY (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Tufts Univ., Medford, MA (United States); UChicago, LLC., Argonne, IL (United States); Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1602429
Alternate Identifier(s):
OSTI ID: 1616953
Grant/Contract Number:  
AC02-06CH11357; FG02-05ER15730; FG02-05ER15731
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 11; Journal Issue: 12; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cao, Sufeng, Yang, Ming, Elnabawy, Ahmed O., Trimpalis, Antonios, Li, Sha, Wang, Chongyang, Göltl, Florian, Chen, Zhihengyu, Liu, Jilei, Shan, Junjun, Li, Mengwei, Haas, Terry, Chapman, Karena W., Lee, Sungsik, Allard, Lawrence F., Mavrikakis, Manos, and Flytzani-Stephanopoulos, Maria. Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions. United States: N. p., 2019. Web. doi:10.1038/s41557-019-0345-3.
Cao, Sufeng, Yang, Ming, Elnabawy, Ahmed O., Trimpalis, Antonios, Li, Sha, Wang, Chongyang, Göltl, Florian, Chen, Zhihengyu, Liu, Jilei, Shan, Junjun, Li, Mengwei, Haas, Terry, Chapman, Karena W., Lee, Sungsik, Allard, Lawrence F., Mavrikakis, Manos, & Flytzani-Stephanopoulos, Maria. Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions. United States. https://doi.org/10.1038/s41557-019-0345-3
Cao, Sufeng, Yang, Ming, Elnabawy, Ahmed O., Trimpalis, Antonios, Li, Sha, Wang, Chongyang, Göltl, Florian, Chen, Zhihengyu, Liu, Jilei, Shan, Junjun, Li, Mengwei, Haas, Terry, Chapman, Karena W., Lee, Sungsik, Allard, Lawrence F., Mavrikakis, Manos, and Flytzani-Stephanopoulos, Maria. Mon . "Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions". United States. https://doi.org/10.1038/s41557-019-0345-3. https://www.osti.gov/servlets/purl/1602429.
@article{osti_1602429,
title = {Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions},
author = {Cao, Sufeng and Yang, Ming and Elnabawy, Ahmed O. and Trimpalis, Antonios and Li, Sha and Wang, Chongyang and Göltl, Florian and Chen, Zhihengyu and Liu, Jilei and Shan, Junjun and Li, Mengwei and Haas, Terry and Chapman, Karena W. and Lee, Sungsik and Allard, Lawrence F. and Mavrikakis, Manos and Flytzani-Stephanopoulos, Maria},
abstractNote = {We report the direct use of inorganometallic gold complexes formed in alkaline solutions as robust heterogeneous catalysts. Specifically, mononuclear gold complexes with the gold atom surrounded by a shell of Na cations through -O- linkages were prepared by dissolving Au(OH)3 in highly alkaline solutions of NaOH. The complexes remain intact upon impregnation onto supports or after drying in air to a crystalline powder. Supported catalysts containing exclusively atomic gold at loadings up to 1.2 wt.% Au were prepared. Either in supported or unsupported form, the mononuclear gold-centered oxo-clusters catalyze the selective methanol dehydrogenation reaction to methyl formate (MF) and hydrogen; a reaction of industrial interest as well as the key step in methanol steam reforming. The [Au1-Ox]- center was identified as the active catalytic site by experimental characterization and density functional theory studies. The methanol dehydrogenation reaction mechanism proceeds via the self-coupling of methanol to MF. No oxygen supply is necessary. Hence, hydrogen rather than water is produced at 2:1 (stoichiometric) molar ratio to MF. The dried crystalline powder of the solution was used as an unsupported catalyst, showing the same chemistry as the supported clusters. Ab initio molecular dynamics (AIMD) simulations of methanol self-coupling on the mononuclear gold clusters revealed the formation of formate spectators on the clusters under reaction conditions, also corroborated by in situ DRIFTS. The inclusion of these spectators proved crucial towards the accurate description of the energetics of self-coupling of methanol on these clusters, thus unravelling the nature of the active site. Catalyst stability up to 250-300 oC in reaction conditions is demonstrated.},
doi = {10.1038/s41557-019-0345-3},
journal = {Nature Chemistry},
number = 12,
volume = 11,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Fig. 1 Fig. 1: Single-atom-gold oxo-clusters in solution, as dried powder, and on TiO2 support. (a) X-ray pair distribution function (PDF) data of the fresh Au1-Ox-Na9-(OH)y and Au1-Ox-K6-(OH)y; following modeling and subtraction of bulk metallic Au impurities; (b) AC-HAADF/STEM image of unsupported Au1-O3-Na9-(OH)9, showing the presence of single gold atoms; (c) Aumore » LIII XANES spectra of the complex in solution; in dried powder form; and supported on titania (0.5 and 1.0 wt.% Au). A 4.8 wt.% Au/TiO2 made by deposition-precipitation (DP) is shown for comparison. Au(OH)3 and gold foil were used as references for AuIII and Au0, respectively. The 1st shell coordination numbers shown for each sample were extracted from the EXAFS fitting results (Supplementary Table 1); (d & e) AC-HAADF-STEM images of the 0.5 wt.% Au1-Ox-Na9- (OH)y/TiO2 (d) and 1.0 wt.% Au1-Ox-Na9-(OH)y/TiO2 (e) catalysts. Single atoms of gold seen as bright contrast dots (~0.2-0.3 nm) are shown circled.« less

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