Inorganic Chemistry Communications
Short communication
Palladium on carbon as an efficient, durable and economical catalyst for the
alcoholysis of B2pin2
,
,
,
,c,*
Junjie Zhoua 1, Ning Lia 1, Jialu Shena, Xu Mengb *, Xiang Liua
a College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, Analysis and Testing Center,
China Three Gorges University, Yichang, Hubei 443002, China
b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of
Sciences, Lanzhou 730000, China
c Yichang Lijia Technology Co, Ltd, Yichang, Hubei 443002, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Pd/C
Hydrogen has attracted much attention as one of the most promising chemical fuel candidates because of its zero
emission during consumption. In order to solve the freezing problem of water based hydrolysis process, herein,
the Pd/C as an efficient and stable catalyst for the methanolysis, ethanolysis, propanolysis and butanolysis of
B2pin2
Alcoholysis
H2
B2pin2 for the generation of hydrogen has been first developed. The large kinetic isotope effect (KIE) of kH/kD
=
5.0, D2 formation from CD3OD and in situ tandem reaction have confirmed that alcohol is the only hydrogen
source. Interestingly, the order of Ea of these alcohols in H2 evolution is MeOH (methanol, 29.57 kJ/mol) < EtOH
(ethanol, 34.80 kJ/mol) < PrOH (propanol, 39.08 kJ/mol) < nBuOH (n-butanol, 41.98 kJ/mol), which is
consistent with the known order of acidities of these alcohols (MeOH > EtOH > PrOH > nBuOH).
Tandem reaction
1. Introduction
Among them, alcoholysis of NH3BH3, NaBH4 or related boron com-
pounds producing H2 with only one H atom provided by alcohol and the
The 21st century, H2 has been regarded as one of the most promising
alternatives to fossil fuels due to its high energy density, sustainability
and zero pollution [1–5]. So, a large deal of researches have been
devoted to H2 evolution upon the hydrolysis of various hydrogen storage
materials, such as dimethylamine-borane, sodium borohydride, hydra-
zine borane, hydrazine hydrate, formic acid and ammonia borane
[6–18]. However, it is still a challenge to develop the hydrolysis of
hydrogen storage materials at subzero temperature (the freezing point of
water is only 0 ◦C).
other one by boron compounds [28–32].
(1)
In fact, our group has a long term active interest in the exploration of
new H2 evolution system [33]. For example, in 2020, our group reported
the H2 evlution upon hydrolysis of tetrahydroxydiboron catalyzed by
graphene quantum dot-stabilized transition metal nanoparticles, in
which both atoms of H2 evolution are provided by H2O [33a]. Herein,
we report Pd/C-catalyzed H2 or D2 evolution from alcoholysis of B2pin2,
in which both two H atoms are obtained from alcohols (including MeOH,
EtOH, PrOH, and nBuOH (Eq. (1)). Among them, B2pin2 is typically used
as a current borylation source [34–38], and rarely applied in the
reduction reactions [39–41]. According to our knowledge, it is the first
systematic research of H2 evolution from the alcoholysis of B2pin2,
although Prabhu and Stoke mentioned that H2 gas could be released
Recently, the H2 evolution upon alcoholysis of hydrogen storage
materials have attracted considerable attention, because it perfectly
solves the freezing problem of water based hydrolysis process
[12,19–24]. In general, NH3 is released along with H2 gas in the hy-
drolysis of hydrogen storage materials. Whereas NH3 is not released in
the alcoholysis of hydrogen storage materials [25–26], thus pure H2 is
formed. Furthermore, the by-products of alcoholysis reaction, such as
NH4B(OCH3)4 and NaB(OCH3)4, can be easily reconverted into
hydrogen storage materials by reaction with LiAlH4 and NH4Cl [27].
* Corresponding authors at: College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials,
Analysis and Testing Center, China Three Gorges University, Yichang, Hubei 443002, China (X. Liu).
1
These authors have equally contributed to this work and should be considered as co-first authors.
Received 10 April 2021; Received in revised form 31 May 2021; Accepted 31 May 2021
Available online 10 June 2021
1387-7003/© 2021 Elsevier B.V. All rights reserved.