Subscriber access provided by UNIV OF TEXAS DALLAS
Communication
Thermal emitting strategy to synthesize atomically dispersed Pt metal sites from bulk Pt metal Yunteng Qu, Bingxu Chen, Zhijun Li, Xuezhi Duan, Liguang Wang, Yue Lin, Tongwei Yuan, Fangyao Zhou, Yidong Hu, Zhengkun Yang, Changming Zhao, Jing Wang, Chao Zhao, Yanmin Hu, Geng Wu, Qinghua Zhang, Qian Xu, Bingyao Liu, Peng Gao, Rui You, Weixin Huang, Lirong Zheng, Lin Gu, Yuen Wu, and Yadong Li J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b09834 • Publication Date (Web): 05 Mar 2019 Downloaded from http://pubs.acs.org on March 5, 2019
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 5 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
Journal of the American Chemical Society
ACS Paragon Plus Environment
Journal of the American Chemical Society 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
Proposed reaction mechanism for the preparation of Pt SAs/DG. 819x370mm (150 x 150 DPI)
ACS Paragon Plus Environment
Page 2 of 5
Page 3 of 5 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
Journal of the American Chemical Society
Thermal Emitting Strategy to Synthesize Atomically Dispersed Pt Metal Sites from Bulk Pt Metal Yunteng Qu,1,† Bingxu Chen,3,† Zhijun Li,1,† Xuezhi Duan3,*,Liguang Wang,4 Yue Lin,5 Tongwei Yuan,6 Fangyao Zhou,1 Yidong Hu,1 Zhengkun Yang,1 Changming Zhao,1 Jing Wang,1 Chao Zhao,1 Yanmin Hu,1 Geng Wu,1 Qinghua Zhang,7 Qian Xu,8 Bingyao Liu,10 Peng Gao,10,11 Rui You,1,5 Weixin Huang, 1,5 Lirong Zheng,9 Lin Gu,7 Yuen Wu1,*, Yadong Li2 1School
of Chemistry and Materials Science, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China; 2Department of Chemistry, Tsinghua University, Beijing 100084, China; 3State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, China; 4Department of Physics, City University of Hong Kong, Hong Kong, China; 5CAS Key Laboratory of Materials for Energy Conversion and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China; 6NEST Lab, Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, PR China; 7Institute of Physics, Chinese Academy of Sciences, Beijing 100190, P. R. China; 8National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230026, China; 9Institute of High Energy Physics, Beijing, China; 10Electron Microscopy Laboratory and International Center for Quantum Materials, School of Physics, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China; 11Collaborative Innovation Centre of Quantum Matter, Beijing 100871, China. Supporting Information Placeholder ABSTRACT: Developing a facile route to access active and well-defined single atom sites catalysts has been a major area of focus for single atoms catalysts (SACs). Herein, we demonstrate a simple approach to generate atomically dispersed platinum via a thermal emitting method using bulk Pt metal as a precursor, significantly simplifying synthesis routes and minimizing synthesis costs. The ammonia produced by pyrolysis of dicyandiamide can coordinate with platinum atoms by strong coordination effect. Then, the volatile Pt(NH3)x can be anchored onto the surface of defective graphene. The asprepared Pt SAs/DG exhibits high activity for the electrochemical hydrogen evolution reaction and selective oxidation of various organosilanes. This viable thermal emitting strategy can also be applied to other single metal atoms, for example, gold and palladium. Our findings provide an enabling and versatile platform for facile accessing SACs towards many industrial important reactions.
Single-atom catalysts (SACs) have become an area of growing scientific interest owing to their maximum atom efficiency and highly catalytic performance.1-9 Recently, some synthetic strategies have been reported to fabricate SACs. In particular, wet-chemical approaches, including coprecipitation and impregnation methods etc., are widely employed because of their low cost and ease of operation.10-12 However, these
approaches suffer from the drawbacks of fusion/aggregation of metal species during the synthetic processes, which greatly hinders their practical applications. Furthermore, other synthetic strategies, such as atomic layer deposition (ALD)13 and mass-selected soft landing14, commonly require expensive equipment with low yields, which are not feasible for largescale production. Therefore, development of a facile and practical strategy for the synthesis of SACs with high activity and well-defined sites is particularly attractive in the field. Recently, only a few top-down strategies have been reported for preparing SACs using metal nanoparticles as the precursor.15 These works involve the transformation from nanoparticles to single atoms under thermal treatment, simplifying the synthesis routes for SACs.16, 17 Currently, our group demonstrated that the Ni atoms of Ni foil could diffuse into the melamine film, forming hierarchical carbon papers with the existence of Ni SAs and Ni NPs.18 Nevertheless, direct fabrication of SACs from bulk noble metal materials have been rarely reported. Herein, we demonstrate a facile thermal emitting strategy to synthesize Pt single sites catalyst directly from bulk Pt net. The preparation procedure and proposed formation mechanism are shown in Figure 1a and Figure S1. Dicyandiamide (DCD), Pt net and graphene oxidation (GO) were sequentially placed in a porcelain boat with Ar flow and then the porcelain boat was heated to 1100 °C. Under high temperature, the DCD underwent a pyrolysis process to generate ammonia gas.19, 20
ACS Paragon Plus Environment
Journal of the American Chemical Society 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
Based on strong coordination interaction between ammonia and Pt atoms, the possible volatile Pt(NH3)x species were formed. Meanwhile, the Pt0 species may be oxidized by oxygencontaining functional group on the surface of GO, forming Ptδ+ (0
