Aqueous Synthesis of Concave Rh Nanotetrahedra with Defect-Rich Surfaces: Insights into Growth-, Defect-, and Plasmon-Enhanced Catalytic Energy Conversion

Kuo, Chin-Sheng; Kao, Chen-Rui; Chen, Wei-Jie; Lu, Ming-Yen; Cullen, David A.; Sneed, Brian T.; Chuang, Yu-Chun; Yu, Ching-Ching; Kuo, Chun-Hong

doi:10.1021/acs.chemmater.8b02003

Title: Aqueous Synthesis of Concave Rh Nanotetrahedra with Defect-Rich Surfaces: Insights into Growth-, Defect-, and Plasmon-Enhanced Catalytic Energy Conversion

Journal Article · Thu Jun 07 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b02003· OSTI ID:1490602

Kuo, Chin-Sheng ^[1]; Kao, Chen-Rui ^[2]; Chen, Wei-Jie ^[3];

^[4];

^[5];

^[5]; Chuang, Yu-Chun ^[6];

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^[8]

Institute of Chemistry, Academia Sinica, Taipei (Taiwan)
Institute of Chemistry, Academia Sinica, Taipei (Taiwan); National Chung Cheng University, Chiayi (Taiwan)
Institute of Chemistry, Academia Sinica, Taipei (Taiwan); National Taiwan Univ., Taipei (Taiwan)
National Tsing Hua University, Hsinchu (Taiwan)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
National Chung Cheng University, Chiayi (Taiwan)
Institute of Chemistry, Academia Sinica, Taipei (Taiwan); National Central University, Jhongli (Taiwan)

The control of morphology in the synthesis of Rh nanocrystals can be used to precisely tailor the electronic surface structure; this in turn directly influences their performance in catalysis applications. Many works have brought attention to the development of Rh nanostructures with low-index surfaces, but limited effort has been devoted to the study of high-index and surface defect-enriched nanocrystals as they are not favored by thermodynamics because of the involvement of high-energy surfaces and increased surface-to-volume ratios. Here, we demonstrate an aqueous synthesis of concave Rh nanotetrahedra (CTDs) serving as efficient catalysts for energy conversion reactions. CTDs are surface defect-rich structures that form through a slow growth rate and follow the four-step model of metallic nanoparticle growth. Via the tuning of the surfactant concentration, the morphology of Rh CTDs evolved into highly excavated nanotetrahedra (HETDs) and twinned nanoparticles (TWs). Unlike the CTD surfaces with abundant adatoms and vacancies, HETDs and TWs have more regular surfaces with layered terraces. Each nanocrystal type was evaluated for methanol electrooxidation and hydrogen evolution from hydrolysis of ammonia borane, and the CTDs significantly showed the best catalytic performance because of defect enrichment, which benefits the surface reactivity of adsorbates. In addition, both CTDs and HETDs have strong absorption near the visible light region (382 and 396 nm), for which they show plasmon-enhanced performance in photocatalytic hydrogen evolution under visible light illumination. CTDs are more photoactive than HETDs, likely because of more pronounced localized surface plasmon resonance hot spots. Lastly, this facile aqueous synthesis of large-surface-area, defect-rich Rh nanotetrahedra is exciting for the fields of nanosynthesis and catalysis.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1490602

Journal Information:: Chemistry of Materials, Vol. 30, Issue 13; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 19 works

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