The mechanism of hydrogen donation by bio-acids over metal supported on nitrogen-doped carbon nanotubes


Biomass-derived carboxylic acids (e.g. acetic acid AcOH and formic acid FA) are a green and low-cost hydrogen source to replace hazardous H2 gas in in-situ hydrogenation processes. To date, bio-acids dehydrogenation has been mainly conducted using noble metal catalysts which would negatively impact the process economy, thus development of efficient non-noble metal catalysts for this purpose is highly desirable. In this study, the performance of transition metals supported on nitrogen doped carbon nanotubes was thoroughly evaluated by computational modelling based on Density Functional Theory (DFT). Results revealed that, out of the 10 selected transition metal candidates, molybdenum (Mo) was most active for binding AcOH and a combination of Mo and nitrogen doping significantly enhanced binding to the carboxylic acid molecules compared to pristine carbon nanotubes (CNTs). The newly designed Mo/N-CNT catalysts considerably facilitated the bio-acids decomposition compared to the non-catalytic scenarios by lowering energy barriers. FA distinctly outperformed AcOH in hydrogen donation over Mo/N-CNT catalysts, through its spontaneous cleavage leading to facile hydrogen donation.

Publication DOI:
Divisions: College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Energy and Bioproducts Research Institute (EBRI)
Additional Information: ©2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license ( Funding: The authors would like to acknowledge financial support from the Leverhulme Trust Research Grant (RPG-2017-254) and EPSRC First Grant (EP/R010986/1). The authors are also grateful for computational support from the UK Materials and Molecular Modelling Hub, which is partially funded by the EPSRC (EP/P020194/1), for which access was obtained via the UKCP consortium and funded by EPSRC Grant (EP/ P022561/1). Additional computational resources from the EPSRC under the project UK Consortium on Mesoscale Engineering Sciences (UKCOMES) (Grant No. EP/R029598/1) are also gratefully acknowledged.
Uncontrolled Keywords: Acetic acid,Biomass,Carbon nanotubes,Formic acid,Molybdenum,Catalysis,Process Chemistry and Technology,Physical and Theoretical Chemistry
Publication ISSN: 2468-8231
Last Modified: 30 Apr 2024 07:21
Date Deposited: 11 Nov 2020 12:58
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Related URLs: https://www.sci ... 5526?via%3Dihub (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2021-01
Published Online Date: 2020-11-04
Accepted Date: 2020-10-21
Authors: Zhang, Jiajun
Zhang, Xiaolei
Osatiashtiani, Amin (ORCID Profile 0000-0003-1334-127X)
Hong Luo, Kai
Shen, Dekui
Li, Jun
Bridgwater, Tony (ORCID Profile 0000-0001-7362-6205)



Version: Published Version

License: Creative Commons Attribution

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