Atomically-precise dopant-controlled single cluster catalysis for electrochemical nitrogen reduction

Chuanhao Yao; Na Guo; Shibo Xi; Cong-Qiao Xu; Wei Liu; Xiaoxu Zhao; Jing Li; Hanyan Fang; Jie Su; Zhongxin Chen; Huan Yan; Zhizhan Qiu; Pin Lyu; Cheng Chen; Haomin Xu; Xinnan Peng; Xinzhe Li; Bin Liu; Chenliang Su; Stephen J Pennycook; Cheng-Jun Sun; Jun Li; Chun Zhang; Yonghua Du; Jiong Lu

doi:10.1038/s41467-020-18080-w

Atomically-precise dopant-controlled single cluster catalysis for electrochemical nitrogen reduction

Nat Commun. 2020 Sep 1;11(1):4389. doi: 10.1038/s41467-020-18080-w.

Authors

Chuanhao Yao^#^{1

2}, Na Guo^#³, Shibo Xi^#⁴, Cong-Qiao Xu^#⁵, Wei Liu^{1

6}, Xiaoxu Zhao^{1

7

8}, Jing Li¹, Hanyan Fang^{1

6}, Jie Su^{1

6}, Zhongxin Chen^{1

7}, Huan Yan¹, Zhizhan Qiu^{1

7}, Pin Lyu¹, Cheng Chen^{1

7}, Haomin Xu^{1

6}, Xinnan Peng^{1

6}, Xinzhe Li¹, Bin Liu⁹, Chenliang Su¹⁰, Stephen J Pennycook^{7

8}, Cheng-Jun Sun¹¹, Jun Li^{12

13}, Chun Zhang^{14

15

16}, Yonghua Du^{17

18}, Jiong Lu^{19

20}

Affiliations

¹ Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
² Frontiers Science Center for Flexible Electronics (FSCFE), Shaanxi Institute of Flexible Electronics (SIFE) & Shaanxi Institute of Biomedical Materials and Engineering (SIBME), Northwestern Polytechnical University (NPU), 127 West Youyi Road, 710072, Xi'an, China.
³ Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore, 117542, Singapore.
⁴ Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, 627833, Singapore.
⁵ Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China.
⁶ Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore, 117546, Singapore.
⁷ NUS Graduate School for Integrative Sciences and Engineering, National University of Singapore, 28 Medical Drive, Singapore, 117456, Singapore.
⁸ Department of Materials Science & Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore, 117575, Singapore.
⁹ School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, Singapore.
¹⁰ SZU-NUS Collaborative Centre and International Collaborative Laboratory of 2D Materials for Optoelectronic Science & Technology, College of Optoelectronic Engineering, Shenzhen University, 518060, Shenzhen, China.
¹¹ Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL, 60439, USA.
¹² Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China. junli@tsinghua.edu.cn.
¹³ Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, 100084, Beijing, China. junli@tsinghua.edu.cn.
¹⁴ Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore. phyzc@nus.edu.sg.
¹⁵ Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore, 117542, Singapore. phyzc@nus.edu.sg.
¹⁶ Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore, 117546, Singapore. phyzc@nus.edu.sg.
¹⁷ Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, 627833, Singapore. ydu@bnl.gov.
¹⁸ National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, 11973, USA. ydu@bnl.gov.
¹⁹ Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore. chmluj@nus.edu.sg.
²⁰ Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore, 117546, Singapore. chmluj@nus.edu.sg.

^# Contributed equally.

Abstract

The ability to precisely engineer the doping of sub-nanometer bimetallic clusters offers exciting opportunities for tailoring their catalytic performance with atomic accuracy. However, the fabrication of singly dispersed bimetallic cluster catalysts with atomic-level control of dopants has been a long-standing challenge. Herein, we report a strategy for the controllable synthesis of a precisely doped single cluster catalyst consisting of partially ligand-enveloped Au₄Pt₂ clusters supported on defective graphene. This creates a bimetal single cluster catalyst (Au₄Pt₂/G) with exceptional activity for electrochemical nitrogen (N₂) reduction. Our mechanistic study reveals that each N₂ molecule is activated in the confined region between cluster and graphene. The heteroatom dopant plays an indispensable role in the activation of N₂ via an enhanced back donation of electrons to the N₂ LUMO. Moreover, besides the heteroatom Pt, the catalytic performance of single cluster catalyst can be further tuned by using Pd in place of Pt as the dopant.

Abstract

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