3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity

Qiao, Zhi; Hwang, Sooyeon; Li, Xing; Wang, Chenyu; Samarakoon, Widitha; Karakalos, Stavros; Li, Dongguo; Chen, Mengjie; He, Yanghua; Wang, Maoyu; Liu, Zhenyu; Wang, Guofeng; Zhou, Hua; Feng, Zhenxing; Su, Dong; Spendelow, Jacob Schatz; Wu, Gang

doi:10.1039/C9EE01899A

Title: 3D porous graphitic nanocarbon for enhancing the performance and durability of Pt catalysts: a balance between graphitization and hierarchical porosity

Journal Article · 15 July 2019 · Energy & Environmental Science

DOI: https://doi.org/10.1039/C9EE01899A · OSTI ID:1581280

Qiao, Zhi ^[1]; Hwang, Sooyeon ^[2]; Li, Xing ^[2];

^[3]; Samarakoon, Widitha ^[4];

^[5];

^[3]; Chen, Mengjie ^[1];

^[1]; Wang, Maoyu ^[4]; Liu, Zhenyu ^[6]; Wang, Guofeng ^[6]; Zhou, Hua ^[7];

^[4]; Su, Dong ^[2];

^[3];

^[1]

State Univ. of New York, Buffalo, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Oregon State Univ., Corvallis, OR (United States)
Univ. of South Carolina, Columbia, SC (United States)
Univ. of Pittsburgh, PA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Carbon supports used in oxygen-reduction cathode catalysts for proton exchange membrane fuel cells (PEMFCs) are vulnerable to corrosion under harsh operating conditions, leading to poor performance durability. To address this issue, we have developed highly stable porous graphitic carbon (PGC) produced through pyrolysis of a 3D polymer hydrogel in combination with Mn. The resulting PGC features multilayer carbon sheets assembled in porous and flower-like morphologies. In situ high-temperature electron microscopy was employed to dynamically monitor the carbonization process up to 1100 °C, suggesting that the 3D polymer hydrogel provides high porosity at multiple scales, and that Mn catalyzes the graphitization process more effectively than other metals. Compared to conventional carbon supports such as Vulcan, Ketjenblack, and graphitized carbon, PGC provides an improved balance between high graphitization and hierarchical porosity, which is favorable for uniform Pt nanoparticle dispersion and enhanced corrosion resistance. As a result, Pt supported on PGC exhibits remarkably enhanced stability. In addition to thorough testing in aqueous electrolytes, we also conducted fuel cell testing using durability protocols recommended by the U.S. Department of Energy (DOE). After 5000 voltage cycles from 1.0 to 1.5 V, the Pt/PGC catalyst only lost 9 mV at a current density of 1.5 A cm^-2, dramatically exceeding the DOE support durability target (<30 mV), and surpassing commercial Pt/C catalysts. Along with the enhanced carbon corrosion resistance of the PGC support, the enhanced catalyst–support interactions are beneficial for stability improvement, likely due to nitrogen doping into carbon, which was further elucidated through X-ray absorption spectroscopy and density functional theory (DFT) calculations. Finally, the high stability and activity of PGC-based Pt catalysts are attributed to the combination of high graphitization degree, favorable surface area and porosity, and nitrogen doping, which effectively stabilize highly dispersed Pt nanoparticles.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001; AC02-06CH11357; SC0012704

OSTI ID:: 1581280

Alternate ID(s):: OSTI ID: 1543417; OSTI ID: 1545900; OSTI ID: 1573498

Report Number(s):: LA-UR-19-27316; BNL-211914-2019-JAAM; EESNBY

Journal Information:: Energy & Environmental Science, Vol. 12, Issue 9; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 183 works

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