State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

Zizwe A Chase; Stanislav Kasakov; Hui Shi; Aleksei Vjunov; John L Fulton; Donald M Camaioni; Mahalingam Balasubramanian; Chen Zhao; Yong Wang; Johannes A Lercher

doi:10.1002/chem.201502723

State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

Chemistry. 2015 Nov 9;21(46):16541-6. doi: 10.1002/chem.201502723. Epub 2015 Sep 25.

Authors

Zizwe A Chase^{1

2}, Stanislav Kasakov³, Hui Shi¹, Aleksei Vjunov¹, John L Fulton⁴, Donald M Camaioni⁵, Mahalingam Balasubramanian⁶, Chen Zhao^{1

2

7}, Yong Wang^{1

2}, Johannes A Lercher^{8

9}

Affiliations

¹ Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA).
² School of Chemical and Biological Engineering, Washington State University, Pullman, WA 99364 (USA).
³ Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4, 85748 Garching (Germany).
⁴ Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA). john.fulton@pnnl.gov.
⁵ Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA). donald.camaioni@pnnl.gov.
⁶ Advanced Photon Source, Argonne National Laboratory, Building 401, 9700 S. Cass Avenue, Argonne, IL 60439 (USA).
⁷ Current address: Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, North Zhongshan Road 3663, 200062 Shanghai (P. R. China).
⁸ Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (USA). johannes.lercher@pnnl.gov.
⁹ Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4, 85748 Garching (Germany). johannes.lercher@pnnl.gov.

PMID: 26407246
DOI: 10.1002/chem.201502723

Abstract

The state of Ni supported on HZSM-5 zeolite, silica, and sulfonated carbon was studied during aqueous-phase catalysis of phenol hydrodeoxygenation using in situ extended X-ray absorption fine structure spectroscopy. On sulfonated carbon and HZSM-5 supports, NiO and Ni(OH)2 were readily reduced to Ni(0) under reaction conditions (≈35 bar H2 in aqueous phenol solutions containing up to 0.5 wt. % phosphoric acid at 473 K). In contrast, Ni supported on SiO2 was not stable in a fully reduced Ni(0) state. Water enables the formation of Ni(II) phyllosilicate, which is more stable, that is, difficult to reduce, than either α-Ni(OH)2 or NiO. Leaching of Ni from the supports was not observed over a broad range of reaction conditions. Ni(0) particles on HZSM-5 were stable even in presence of 15 wt. % acetic acid at 473 K and 35 bar H2 .

Keywords: EXAFS; XANES; hydrogenation; nanoparticles; nickel.