title: Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer-Tropsch Synthesis.
abstract: Ruthenium is a promising low-temperature catalyst for Fischer-Tropsch synthesis (FTS). However, its scarcity and modest specific activity limit its widespread industrialization. We demonstrate here a strategy for tuning the crystal phase of catalysts to expose denser and active sites for a higher mass-specific activity. Density functional theory calculations show that upon CO dissociation there are a number of open facets with modest barrier available on the face-centered cubic (fcc) Ru but only a few step edges with a lower barrier on conventional hexagonal-closest packed (hcp) Ru. Guided by theoretical calculations, water-dispersible fcc Ru catalysts containing abundant open facets were synthesized and showed an unprecedented mass-specific activity in the aqueous-phase FTS, 37.8 molCO·molRu-1·h-1at 433 K. The mass-specific activity of the fcc Ru catalysts with an average size of 6.8 nm is about three times larger than the previous best hcp catalyst with a smaller size of 1.9 nm and a higher specific surface area. The origin of the higher mass-specific activity of the fcc Ru catalysts is identified experimentally from the 2 orders of magnitude higher density of the active sites, despite its slightly higher apparent barrier. Experimental results are in excellent agreement with prediction of theory. The great influence of the crystal phases on site distribution and their intrinsic activities revealed here provides a rationale design of catalysts for higher mass-specific activity without decrease of the particle size.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Wei-Zhen
authors.initials: WZ
authors.lastname: Li
authors.affiliation: Department of Chemical Physics, College of Chemistry and Materials Science, iChEM, CAS Center for Excellence in Nanoscience, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026, China.|State Key Laboratory of Catalysis, State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Jin-Xun
authors.initials: JX
authors.lastname: Liu
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Gu
authors.affiliation: School of Physical Sciences, CAS Key Laboratory of Vacuum Sciences, University of Chinese Academy of Sciences , Beijing 100049, China.|Materials Science and Technology Division, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Wu
authors.initials: W
authors.lastname: Zhou
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Si-Yu
authors.initials: SY
authors.lastname: Yao
authors.affiliation: Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences , Shanghai 201204, China.
authors.forename: Rui
authors.initials: R
authors.lastname: Si
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Guo
authors.affiliation: State Key Laboratory of Catalysis, State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Hai-Yan
authors.initials: HY
authors.lastname: Su
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Chun-Hua
authors.initials: CH
authors.lastname: Yan
authors.affiliation: Department of Chemical Physics, College of Chemistry and Materials Science, iChEM, CAS Center for Excellence in Nanoscience, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China , Hefei 230026, China.|State Key Laboratory of Catalysis, State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Wei-Xue
authors.identifier: 0000-0002-5043-3088
authors.initials: WX
authors.lastname: Li
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Ya-Wen
authors.initials: YW
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
authors.forename: Ding
authors.identifier: 0000-0002-3341-2998
authors.initials: D
authors.lastname: Ma