Highly Crystalline and Porous Borocarbonitrides as Metal-Free Catalysts for Boosted N-Heterocycle Dehydrogenation

Qingju Wang; Kevin Siniard; Shuai Yuan; Nikolaos Samartzis; Tao Wang; Xin Wang; Long Qi; Takeshi Kobayashi; Yonghee Lee; Jinghua Guo; Alexander S. Ivanov; Leighanne C. Gallington; Xiao Tong; Lilin He; Gergely Nagy; Murillo L. Martins; Yongqiang Cheng; De en Jiang; Zhenzhen Yang; Sheng Dai

doi:10.1002/anie.5627455

Highly Crystalline and Porous Borocarbonitrides as Metal-Free Catalysts for Boosted N-Heterocycle Dehydrogenation

Qingju Wang
, Kevin Siniard
, Shuai Yuan
, Nikolaos Samartzis
, Tao Wang
, Xin Wang
, Long Qi
, Takeshi Kobayashi
, Yonghee Lee
, Jinghua Guo
, Alexander S. Ivanov
, Leighanne C. Gallington
, Xiao Tong
, Lilin He
, Gergely Nagy
, Murillo L. Martins
, Yongqiang Cheng
, De en Jiang
, Zhenzhen Yang
, Sheng Dai

Research output: Contribution to journal › Article › peer-review

Abstract

Safe and efficient hydrogen storage is pivotal for enabling a clean hydrogen economy. Liquid organic hydrogen carriers (LOHCs) offer a practical solution, but their deployment is hindered by the lack of highly active and economical dehydrogenation catalysts. Here, we report a metal-free catalyst design that overcomes the long-standing trade-off between crystallinity and surface area in two-dimensional frameworks for highly efficient dehydrogenation of LOHCs. A flux-assisted reconstruction strategy transforms amorphous borocarbonitrides (AM-BCN) into highly crystalline, defect-rich BCN nanosheets (C-BCN) with large surface area and accessible porosity, as confirmed by complementary spectroscopic, x-ray, and neutron analyses. C-BCN catalyzes the acceptor-less dehydrogenation of aza-fused LOHCs with quantitative hydrogen release under mild conditions, outperforming AM-BCN and previously reported metal-free scaffolds. Mechanistic insights from x-ray, neutron scattering, and theoretical calculations identify open C-B-N and N-B-N defect motifs as the primary active sites. This work establishes a generalizable strategy to engineer crystalline, porous, defect-rich two-dimensional lattices and demonstrates a highly active metal-free platform for LOHC dehydrogenation with high-purity H₂ generation.

Original language	English
Article number	e5627455
Journal	Angewandte Chemie - International Edition
Volume	65
Issue number	24
DOIs	https://doi.org/10.1002/anie.5627455
State	Published - Jun 8 2026

Funding

The research was supported financially by the U.S. Department of Energy, Office of Energy Efficiency, and Renewable Energy (EERE): DE‐EE0011097. This work was financially supported by the Hydrogen Materials Advanced Research Consortium (HyMARC), established as part of the Energy Materials Network by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, under Contract Number DE‐AC02‐05CH11231. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Oak Ridge National Laboratory is managed by UT‐Battelle, LLC, for U.S. DOE under Contract No. DEAC05‐00OR22725. The beam time was allocated to EQ‐SANS, BL‐6, on proposal number IPTS‐36295 and to VISION, BL‐16B, on proposal number IPTS‐35966. This research was performed on APS beam time award: https://doi.org/10.46936/APS‐188511/60013158 , from the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE‐AC02‐05CH11231. S.Y. and D.J. (Vanderbilt, DFT computation) and K.T. and L.Q. (Ames Lab) were supported by their individual projects funded by U.S. Department of Energy, Oﬃce of Science, Oﬃce of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program. Ames National Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DEAC02‐07CH11358. The research was supported financially by the U.S. Department of Energy, Office of Energy Efficiency, and Renewable Energy (EERE): DE-EE0011097. This work was financially supported by the Hydrogen Materials Advanced Research Consortium (HyMARC), established as part of the Energy Materials Network by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, under Contract Number DE-AC02-05CH11231. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for U.S. DOE under Contract No. DEAC05-00OR22725. The beam time was allocated to EQ-SANS, BL-6, on proposal number IPTS-36295 and to VISION, BL-16B, on proposal number IPTS-35966. This research was performed on APS beam time award: https://doi.org/10.46936/APS-188511/60013158, from the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. S.Y. and D.J. (Vanderbilt, DFT computation) and K.T. and L.Q. (Ames Lab) were supported by their individual projects funded by U.S. Department of Energy, Oﬃce of Science, Oﬃce of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program. Ames National Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DEAC02-07CH11358.

Keywords

borocarbonitride
dehydrogenation
flux reconstruction
liquid organic hydrogen carriers
metal-free catalysts

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10.1002/anie.5627455

Cite this

Wang, Q., Siniard, K., Yuan, S., Samartzis, N., Wang, T., Wang, X., Qi, L., Kobayashi, T., Lee, Y., Guo, J., Ivanov, A. S., Gallington, L. C., Tong, X., He, L., Nagy, G., Martins, M. L., Cheng, Y., Jiang, D. E., Yang, Z., & Dai, S. (2026). Highly Crystalline and Porous Borocarbonitrides as Metal-Free Catalysts for Boosted N-Heterocycle Dehydrogenation. Angewandte Chemie - International Edition, 65(24), Article e5627455. https://doi.org/10.1002/anie.5627455

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title = "Highly Crystalline and Porous Borocarbonitrides as Metal-Free Catalysts for Boosted N-Heterocycle Dehydrogenation",

abstract = "Safe and efficient hydrogen storage is pivotal for enabling a clean hydrogen economy. Liquid organic hydrogen carriers (LOHCs) offer a practical solution, but their deployment is hindered by the lack of highly active and economical dehydrogenation catalysts. Here, we report a metal-free catalyst design that overcomes the long-standing trade-off between crystallinity and surface area in two-dimensional frameworks for highly efficient dehydrogenation of LOHCs. A flux-assisted reconstruction strategy transforms amorphous borocarbonitrides (AM-BCN) into highly crystalline, defect-rich BCN nanosheets (C-BCN) with large surface area and accessible porosity, as confirmed by complementary spectroscopic, x-ray, and neutron analyses. C-BCN catalyzes the acceptor-less dehydrogenation of aza-fused LOHCs with quantitative hydrogen release under mild conditions, outperforming AM-BCN and previously reported metal-free scaffolds. Mechanistic insights from x-ray, neutron scattering, and theoretical calculations identify open C-B-N and N-B-N defect motifs as the primary active sites. This work establishes a generalizable strategy to engineer crystalline, porous, defect-rich two-dimensional lattices and demonstrates a highly active metal-free platform for LOHC dehydrogenation with high-purity H2 generation.",

keywords = "borocarbonitride, dehydrogenation, flux reconstruction, liquid organic hydrogen carriers, metal-free catalysts",

author = "Qingju Wang and Kevin Siniard and Shuai Yuan and Nikolaos Samartzis and Tao Wang and Xin Wang and Long Qi and Takeshi Kobayashi and Yonghee Lee and Jinghua Guo and Ivanov, \{Alexander S.\} and Gallington, \{Leighanne C.\} and Xiao Tong and Lilin He and Gergely Nagy and Martins, \{Murillo L.\} and Yongqiang Cheng and Jiang, \{De en\} and Zhenzhen Yang and Sheng Dai",

note = "Publisher Copyright: {\textcopyright} 2026 Wiley-VCH GmbH.",

year = "2026",

month = jun,

day = "8",

doi = "10.1002/anie.5627455",

language = "English",

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Wang, Q, Siniard, K, Yuan, S, Samartzis, N, Wang, T, Wang, X, Qi, L, Kobayashi, T, Lee, Y, Guo, J, Ivanov, AS, Gallington, LC, Tong, X, He, L , Nagy, G , Martins, ML , Cheng, Y, Jiang, DE, Yang, Z & Dai, S 2026, 'Highly Crystalline and Porous Borocarbonitrides as Metal-Free Catalysts for Boosted N-Heterocycle Dehydrogenation', Angewandte Chemie - International Edition, vol. 65, no. 24, e5627455. https://doi.org/10.1002/anie.5627455

TY - JOUR

T1 - Highly Crystalline and Porous Borocarbonitrides as Metal-Free Catalysts for Boosted N-Heterocycle Dehydrogenation

AU - Wang, Qingju

AU - Siniard, Kevin

AU - Yuan, Shuai

AU - Samartzis, Nikolaos

AU - Wang, Tao

AU - Wang, Xin

AU - Qi, Long

AU - Kobayashi, Takeshi

AU - Lee, Yonghee

AU - Guo, Jinghua

AU - Ivanov, Alexander S.

AU - Gallington, Leighanne C.

AU - Tong, Xiao

AU - He, Lilin

AU - Nagy, Gergely

AU - Martins, Murillo L.

AU - Cheng, Yongqiang

AU - Jiang, De en

AU - Yang, Zhenzhen

AU - Dai, Sheng

PY - 2026/6/8

Y1 - 2026/6/8

N2 - Safe and efficient hydrogen storage is pivotal for enabling a clean hydrogen economy. Liquid organic hydrogen carriers (LOHCs) offer a practical solution, but their deployment is hindered by the lack of highly active and economical dehydrogenation catalysts. Here, we report a metal-free catalyst design that overcomes the long-standing trade-off between crystallinity and surface area in two-dimensional frameworks for highly efficient dehydrogenation of LOHCs. A flux-assisted reconstruction strategy transforms amorphous borocarbonitrides (AM-BCN) into highly crystalline, defect-rich BCN nanosheets (C-BCN) with large surface area and accessible porosity, as confirmed by complementary spectroscopic, x-ray, and neutron analyses. C-BCN catalyzes the acceptor-less dehydrogenation of aza-fused LOHCs with quantitative hydrogen release under mild conditions, outperforming AM-BCN and previously reported metal-free scaffolds. Mechanistic insights from x-ray, neutron scattering, and theoretical calculations identify open C-B-N and N-B-N defect motifs as the primary active sites. This work establishes a generalizable strategy to engineer crystalline, porous, defect-rich two-dimensional lattices and demonstrates a highly active metal-free platform for LOHC dehydrogenation with high-purity H2 generation.

AB - Safe and efficient hydrogen storage is pivotal for enabling a clean hydrogen economy. Liquid organic hydrogen carriers (LOHCs) offer a practical solution, but their deployment is hindered by the lack of highly active and economical dehydrogenation catalysts. Here, we report a metal-free catalyst design that overcomes the long-standing trade-off between crystallinity and surface area in two-dimensional frameworks for highly efficient dehydrogenation of LOHCs. A flux-assisted reconstruction strategy transforms amorphous borocarbonitrides (AM-BCN) into highly crystalline, defect-rich BCN nanosheets (C-BCN) with large surface area and accessible porosity, as confirmed by complementary spectroscopic, x-ray, and neutron analyses. C-BCN catalyzes the acceptor-less dehydrogenation of aza-fused LOHCs with quantitative hydrogen release under mild conditions, outperforming AM-BCN and previously reported metal-free scaffolds. Mechanistic insights from x-ray, neutron scattering, and theoretical calculations identify open C-B-N and N-B-N defect motifs as the primary active sites. This work establishes a generalizable strategy to engineer crystalline, porous, defect-rich two-dimensional lattices and demonstrates a highly active metal-free platform for LOHC dehydrogenation with high-purity H2 generation.

KW - borocarbonitride

KW - dehydrogenation

KW - flux reconstruction

KW - liquid organic hydrogen carriers

KW - metal-free catalysts

UR - https://www.scopus.com/pages/publications/105036605585

U2 - 10.1002/anie.5627455

DO - 10.1002/anie.5627455

M3 - Article

AN - SCOPUS:105036605585

SN - 1433-7851

VL - 65

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 24

M1 - e5627455

ER -

Highly Crystalline and Porous Borocarbonitrides as Metal-Free Catalysts for Boosted N-Heterocycle Dehydrogenation

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Keywords

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