One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading

Zhao, Shiyong; Cheng, Yi; Veder, Jean-Pierre; Johannessen, Bernt; Saunders, Martin; Zhang, Lianji; Liu, Chang; Chisholm, Matthew F.; De Marco, Roland; Liu, Jian; Yang, Shi-Ze; Jiang, San Ping

doi:10.1021/acsaem.8b00903

One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading

Journal Article · Mon Sep 10 00:00:00 EDT 2018 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.8b00903· OSTI ID:1607268

Zhao, Shiyong ^[1]; Cheng, Yi ^[1]; Veder, Jean-Pierre ^[1]; Johannessen, Bernt ^[2]; Saunders, Martin ^[3]; Zhang, Lianji ^[4]; Liu, Chang ^[4]; Chisholm, Matthew F. ^[5]; ^[6]; ^[7]; ^[5]; ^[1]

Curtin Univ., Perth, WA (Australia)
Australian Synchrotron, Clayton, ViIC (Australia)
Univ. of Western Australia, Perth, WA (Australia)
Chinese Academy of Sciences, Shenyang, LN (China)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Sunshine Coast, Maroochydore DC, QLD (Australia); The Univ. of Queensland, Brisbane (Australia)
Univ. of Surrey, Guildford (United Kingdom)

The practical application of single atom catalysts (SACs) is constrained by the low achievable loading of single metal atoms. In this work, nickel SACs stabilized on a nitrogen-doped carbon nanotube structure (NiSA-N-CNT) with ultrahigh Ni atomic loading up to 20.3 wt % have been successfully synthesized using a new one-pot pyrolysis method employing Ni acetylacetonate (Ni(acac)₂) and dicyandiamide (DCD) as precursors. The yield and formation of NiSA-N-CNT depends strongly on the Ni(acac)₂/DCD ratio and annealing temperature. Pyrolysis at 350 and 650 °C led to the formation of Ni single atom dispersed melem and graphitic carbon nitride (Ni-melem and Ni-g-C₃N₄). Transition from a stacked and layered Ni-g-C₃N₄ structure to a bamboo-shaped tubular NiSA-N-CNT structure most likely occurs via a solid-to-solid curling or rolling-up mechanism, thermally activated at temperatures of 700–900 °C. Extended X-ray absorption fine structure (EXAFS) experiments and simulations show that Ni single atoms are stabilized in the N-CNT structure through nitrogen coordination, forming a structure with four nearest N coordination shell surrounded by two carbon shells, Ni–N₄. The NiSA-N-CNT catalysts show an excellent activity and selectivity for the electrochemical reduction of CO₂, achieving a turnover frequency (TOF) of 11.7 s–1 at -0.55 V (vs RHE), but a low activity for the O₂ reduction and O₂ evolution reactions, as compared to Ni nanoparticles supported on N-CNTs.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Sponsoring Organization:: Australian Research Council (ARC); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1607268

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 10 Vol. 1; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading

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