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journal article·2021-09Open access

Zero‐Valent Palladium Single‐Atoms Catalysts Confined in Black Phosphorus for Efficient Semi‐Hydrogenation

Cheng Chen, Wei Ou, Kah‐Meng Yam, Shibo Xi, Xiaoxu Zhao, Si Chen, Jing Li, Pin Lyu, Lu Ma, Yonghua Du, Wei Yu, Hanyan Fang, Chuanhao Yao, Xiao Hai, Haomin Xu, Ming Joo Koh, Stephen J. Pennycook, Junling Lu, Ming Lin, Chenliang Su, Chun Zhang, Jiong Lu

Advanced Materials· Volume 33· Issue 35
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Abstract

Abstract Single‐atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. Here, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd 1 , Pt 1 ) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero‐valent palladium SACs in the vacancy site. Metallic Pd 1 /BP SAC shows a highly selective semi‐hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent‐like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H 2 . Zero‐valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero‐valent SACs on BP for organic transformations.
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Research context

NanomaterialsCatalysis & surfacesMaterials processing

OpenAlex topics: Electrocatalysts for Energy Conversion · Advanced Photocatalysis Techniques · Nanomaterials for catalytic reactions

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry National University of Singapore 3 Science Drive 3 Singapore 117543 Singapore

NUS (Suzhou) Research Institute No. 377 Linquan Street, Suzhou Industrial Park Suzhou Jiangsu 215028 China

SZU‐NUS Collaborative Center International Collaborative Laboratory of 2D Materials for Optoelectronic Science & Technology of Ministry of Education Engineering Technology Research Center for 2D Materials Information Functional Devices and Systems of Guangdong Province Institute of Microscale Optoelectronics Shenzhen University Shen Zhen 518060 China

Centre for Advanced 2D Materials and Graphene Research Centre National University of Singapore Singapore 117546 Singapore

Department of Physics National University of Singapore 2 Science Drive 3 Singapore 117542 Singapore

Institute of Chemical and Engineering Sciences A*STAR (Agency for Science, Technology and Research) 1 Pesek Road, Jurong Island Singapore 627833 Singapore

School of Materials Science and Engineering Nanyang Technological University Singapore 639798 Singapore

Department of Chemical Physics University of Science and Technology of China Hefei 230026 China

National Synchrotron Light Source II Brookhaven National Laboratory Upton NY 11973 USA

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 Xi'an 710072 China

Department of Materials Science & Engineering National University of Singapore 9 Engineering Drive 1 Singapore 117575 Singapore

Institute of Materials Research and Engineering Agency for Science, Technology and Research (A*STAR) 2 Fusionopolis Way, Innovis, #08‐03 Singapore 138634 Singapore

Funding

Ministry of Education · Agency for Science, Technology and Research · Shenzhen Peacock Plan

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