@article{391a2927a01647cd824367a9d1f3cc73,
title = "On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation: A Kinetic Study of Au/MO x Catalysts Prepared from Oleylamine-Capped Colloidal Nanoparticles",
abstract = " We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylamine-capped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ∼2.5 nm in diameter. The catalysts showed high alkene selectivity (>90 %) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25–40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen-bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal-support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1-octyne reaction orders (∼−0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non-competitive activated adsorption of H 2 on an alkyne-covered Au surface.",
author = "Bruno, {James E.} and {Sravan Kumar}, {K. B.} and Dwarica, {Nicolas S.} and Alexander H{\"u}ther and Zhifeng Chen and Guzman, {Clemente S.} and Hand, {Emily R.} and Moore, {William C.} and Rioux, {Robert M.} and Grabow, {Lars C.} and Chandler, {Bert D.}",
note = "Funding Information: J.E.B, N.S.D., A.H., C.S.G., E.R.H, W.C.M, Z.C., R.M.R. and B.D.C. thank the National Science Foundation for funding. K.B.S.K. and L.C.G. also thank the NSF: CHE-CAT #1465184 and CBET #1803769. Z. C. and R. M. R. acknowledge partial support of this work from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences Catalysis Science program, under Award DE-SC0016192. We thank Gary Gildert (Vanguard Catalyst) for supplying the Pd/Al2O3 catalyst, and Prof. Chris Pursell (Trinity University) for helpful discussions and experimental expertise. The computational work used the Extreme Science and Engineering Discovery Environment (XSEDE) clusters Stampede/Stampede 2 at the Texas Advanced Computing Center (TACC) and Comet at the San Diego Supercomputing Center through allocation TG-CHE140109. High performance computational resources at the University of Houston are supported through an MRI award from the National Science Foundation (ACI-1531814), the Center of Advanced Computing and Data Science (CACDS), and the Research Computing Center (RCC). Finally, we thank the following undergraduate researchers from Trinity University for experimental assistance: Todd Whittaker, Stephen Thai, and Daniel Elizondo. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",
year = "2019",
month = mar,
day = "20",
doi = "10.1002/cctc.201801882",
language = "English (US)",
volume = "11",
pages = "1650--1664",
journal = "ChemCatChem",
issn = "1867-3880",
publisher = "Wiley - VCH Verlag GmbH & CO. KGaA",
number = "6",
}