Hydrogen generation via ammonia decomposition on highly efficient and stable Ru-free catalysts: approaching complete conversion at 450 °C

Tabassum, Hassina; Mukherjee, Shreya; Chen, Junjie; Holiharimanana, Domoina; Karakalos, Stavros; Yang, Xiaoxuan; Hwang, Sooyeon; Zhang, Tianyu; Lu, Bo; Chen, Min; Tang, Zhong; Kyriakidou, Eleni A.; Ge, Qingfeng; Wu, Gang

doi:10.1039/d1ee03730g

Title: Hydrogen generation via ammonia decomposition on highly efficient and stable Ru-free catalysts: approaching complete conversion at 450 °C

Journal Article · Tue Aug 16 00:00:00 EDT 2022 · Energy & Environmental Science

DOI:https://doi.org/10.1039/d1ee03730g· OSTI ID:1991174

Tabassum, Hassina ^[1]; Mukherjee, Shreya ^[1];

^[1]; Holiharimanana, Domoina ^[2];

^[3]; Yang, Xiaoxuan ^[1];

^[4]; Zhang, Tianyu ^[2]; Lu, Bo ^[5]; Chen, Min ^[5]; Tang, Zhong ^[5];

^[1]; Ge, Qingfeng ^[2];

^[1]

State University of New York (SUNY), Buffalo, NY (United States)
Southern Illinois University, Carbondale, IL (United States)
University of South Carolina, Columbia, SC (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Bettergy Corporation, Peekskill, NY (United States)

We report Hydrogen (H₂) is a prospective zero-carbon and high-energy-density fuel alternative to fossil fuels for generating power and clean energy. Ammonia (NH₃) is a promising H₂ (17.7%) carrier, which can easily overcome the challenges associated with H₂ storage and transportation. Thermocatalytic ammonia decomposition reaction (ADR) is an effective way to produce clean H₂ but it relies on the use of expensive and rare ruthenium (Ru)-based catalysts at elevated temperatures (>500 °C), hence is not sustainable and economically feasible. Herein, we report a synergistic strategy to design a heterostructured Ru-free catalyst, consisting of CoNi alloy nanoparticles well-dispersed on a MgO–CeO₂–SrO mixed oxide support with potassium promotion. The resulting K–CoNi_alloy–MgO–CeO₂–SrO catalyst presents 97.7% and 87.5% NH₃ conversion efficiency at 450 °C at gas hourly space velocities (GHSVs) of 6000- and 12 000-mL h^-1 g_cat^-1, respectively. At 500 °C, the H₂ production rate (57.75 mmol g_cat^-1 min^-1) becomes comparable to that of most of the reported Ru-based catalysts. The catalyst stability has been successfully demonstrated in both a fixed-bed reactor under high pressure (120 h at 5.0 bar) and a membrane reactor prototype (600 h at 1.5 bar) at 500 °C. High-temperature in situ XPS analysis, temperature-programmed desorption/reduction, and density functional theory calculations have been carried out to elucidate the possible active sites and performance enhancement mechanisms. This work highlights the importance of constructing optimal interfaces between active metal nanoparticles and oxide support for boosting the NH₃ to H₂ conversion efficiency and long-term stability.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); New York State Energy Research and Development Authority (NYSERDA); USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; AR0000817; CBET-1438440

OSTI ID:: 1991174

Alternate ID(s):: OSTI ID: 1884871; OSTI ID: 1888735

Report Number(s):: BNL-223406-2022-JAAM

Journal Information:: Energy & Environmental Science, Vol. 15, Issue 10; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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