Temperature-driven reaction pathways in alkane direct dehydrogenation over metal-free nitrogen doped carbocatalysts

Zhang, Jie; Behera, Ranjan K.; Nguyen, Vy T.; Liu, Zhenhao; Jimenez, Juan D.; Reddy, Kasala Prabhakar; Moncada, Jorge; Jaye, Cherno; Oh, Jinsu; Meng, Chao; Zhou, Lin; Senanayake, Sanjaya D.; Wang, Bin; Qi, Long; Huang, Wenyu

doi:10.1039/d5sc08580b

Title: Temperature-driven reaction pathways in alkane direct dehydrogenation over metal-free nitrogen doped carbocatalysts

Journal Article · Tue Jan 20 00:00:00 UTC 2026 · Chemical Science

DOI: https://doi.org/10.1039/d5sc08580b · OSTI ID:3017611

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Ames Laboratory (AMES), Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States)
Univ. of Oklahoma, Norman, OK (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Ames Laboratory (AMES), Ames, IA (United States)

Metal-free heteroatom-doped carbocatalysts are promising alternatives to precious metals for alkane direct dehydrogenation/hydrogenation and reversible hydrogen storage, yet the nature of their active sites remains poorly understood. This study investigates a nitrogen assembly carbocatalyst (NAC) for efficient and selective hydrocarbon dehydrogenation. For ethylbenzene, NAC maintains a selectivity of >99% towards styrene at a conversion of >20% for 120 hours at a weight hourly space velocity of 0.4 h⁻¹. Theoretical studies suggest that closely spaced graphitic nitrogen sites are the active sites for the chemisorption and dehydrogenation of ethylbenzene, and the robustness of these sites is supported by ambient-pressure X-ray photoelectron spectroscopy. Kinetic analysis reveals a temperature-dependent reaction profile, with distinct activation energies and reaction orders at 300 and 500 °C. Isotope-labeling studies indicate that dehydrogenation primarily proceeds via initial cleavage of the benzylic C–H bond, and the faster desorption of ethylbenzene at higher temperatures contributes to the difference in kinetic behavior. Importantly, the NAC catalyst also enables efficient hydrogenation of styrene back to ethylbenzene at 250 °C, allowing for reversible hydrogen storage using a single catalyst at moderate temperatures. These findings underscore the significance of constructing high densities of closely spaced graphitic nitrogen in carbocatalysts for enhanced activity and selectivity.

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

Sponsoring Organization:: National Science Foundation; National Science Foundation (NSF); U.S. Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-07CH11358; SC0012704

OSTI ID:: 3017611

Report Number(s):: AL-J 1022; BNL--229408-2026-JAAM

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 11 Vol. 17; ISSN 2041-6539; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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