Subscriber access provided by University of Rhode Island | University Libraries
Letter
Alkyne-functionalized ruthenium nanoparticles: impact of metal-ligand interfacial bonding interactions on the selective hydrogenation of styrene Fengqi Zhang, Jingjing Fang, Lin Huang, Wenming Sun, Zhang Lin, Zhenqing Shi, Xiongwu Kang, and Shaowei Chen ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b04028 • Publication Date (Web): 30 Nov 2018 Downloaded from http://pubs.acs.org on November 30, 2018
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 18 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Catalysis
Alkyne-Functionalized Ruthenium Nanoparticles: Impact of Metal-Ligand Interfacial Bonding Interactions on the Selective Hydrogenation of Styrene Fengqi Zhang†,a Jingjing Fang†,a Lin Huang†,a Wenming Sun,b Zhang Lin,c Zhenqing Shi c, Xiongwu Kang*a and Shaowei Chen*a,d a
Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, China
b
State Key Laboratory of Green Building Materials, China Building Materials Academy, Beijing 100041, China c Guangdong
Engineering and Technology Research Center for Environmental Nanomaterials,
School of Environment and Energy, South China University of Technology, Guangzhou, Guangdong 510006, China d Department
of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064, United States * E-mails:
[email protected];
[email protected] † equal contributing authors
ABSTRACT In the present study, ruthenium nanoparticles functionalized with terminal and internal alkynes were prepared and it was found that internal alkynes formed a η2 side-on configuration on ruthenium nanoparticles surface, in sharp contrast to the ruthenium-vinylidene interfacial bonds for terminal alkynes. For the nanoparticles capped with internal alkyne, hydrogenation of 1
ACS Paragon Plus Environment
ACS Catalysis 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
both the vinyl moiety and phenyl ring occurred, whereas selective hydrogenation of the vinyl moiety was observed with terminal alkyne-functionalized nanoparticles. This work highlights the importance of metal-organic interface in the rational design and engineering of nanoparticle catalyst for organic synthesis. KEYWORDS: ruthenium nanoparticles, internal alkyne, η2 side-on configuration, σ-π covalent, interfacial charge transfer, styrene hydrogenation
Introduction Catalysis plays a critical role in the production and transformation of valuable chemicals, where high selectivity towards desired molecules and compounds significantly reduces the amount of chemical wastes generated and represents an important part in the quest for “green chemistries”.1-4 Towards this end, a range of synthetic approaches based on nanotechnology have been reported in recent literatures.5 Among them, surface functionalization of transition metal nanoparticles by selecting organic capping ligands has been demonstrated to be a powerful tool in the manipulation and enhancement of the nanoparticle catalytic performance.6-11 For instance, as one of the capping ligands, terminal alkyne molecules have been demonstrated effective in modulating the catalytic activity of the metal nanoparticles in heterogeneous catalysis. For instance, rod-shaped [Au25(PPh3)10(C≡CPh)5X2]2+ (X = Br, Cl) nanoclusters exhibited selective catalytic activity towards the semi-hydrogenation of terminal alkynes, due to bridging of Au atoms by deprotonated alkynes, while the uncapped Au nanoclusters are active in the hydrogenation of both terminal and internal alkynes.12 In another study,13 the formation of surface staple motifs of PhC≡C−Au−C≡CPh in alkynyl-protected Au34Ag28(PhC ≡ C)34 nanoclusters led to enhanced catalytic performance towards the hydrolytic oxidation of organosilanes to silanols, in comparison to those with the surface ligands partially or completely 2
ACS Paragon Plus Environment
Page 2 of 18
Page 3 of 18 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Catalysis
removed. Wang’s group compared the catalytic activity of alkyne- and thiolate-capped Au38 nanoclusters in the semi-hydrogenation of alkynes to alkenes and observed markedly higher activity of the former (>97%) than that of the latter (
