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Efficient Hydrogen Generation from the NaBH4 Hydrolysis by

Cobalt-Based Catalysts: Positive Roles of Sulfur-Containing Salts
Xianwen Zhang, Qin Zhang, Bin Xu, Xiaoqiang Liu, Kaiming Zhang, Guangyin Fan, and Weidong Jiang*
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ABSTRACT: Development of a simple and efficient strategy for

improving the catalytic activity of cobalt-based catalysts toward
hydrogen evolution from sodium borohydride (NaBH4) is paramount
but remains challenging. Here, we reported a facile and efficient
Downloaded via UNIVERSITY LILLE on August 16, 2022 at 08:02:56 (UTC).

approach to tune the catalytic performance for NaBH4 hydrolysis with

Co-based catalysts prepared by using cobalt sulfate as a precursor or a
mixture of sulfur-containing sodium salts/cobalt salts as a raw material.
With the use of cobalt sulfate as the precursor, the CoSO4-doped
Co3O4 sample was formed and it exhibited excellent activity with the
generation of ∼500 mL of hydrogen gas from NaBH4 hydrolysis under
mild conditions. In terms of sulfur-free cobalt salts (e.g., cobalt chloride,
cobalt nitrate, and cobalt acetate) as precursors, the obtained Co-based
samples were found to be entirely ineffective for hydrogen production.
Interestingly, during the cobalt-based catalyst preparation, the
introduction of sodium sulfate or sodium sulfide can considerably accelerate hydrogen production. On the contrary, adding
sulfur-bearing salts did not inspire any activity improvement only during the hydrogen generation reaction. Control experiments
indicate that during catalyst preparation, the presence of Na2SO4 and Na2S is beneficial for the in situ transformation of Co3O4 into
catalytically active Co−B alloys, accompanying a positive change in surface morphology during the NaBH4 hydrolysis, thereby
inducing an excellent hydrogen generation rate of up to 4425 mL·min−1·gcat−1.
KEYWORDS: sulfur-containing salts, Co-based catalysts, hydrogen production, hydrolysis, sodium borohydride

1. INTRODUCTION LiBH4) is regarded as a convenient, economic, and efficient

At present, hydrogen energy becomes a focus point in the
improvement of alternative clean energy sources because of its
environment-friendly performance and high energy density1−3
in comparison with those traditional fossil fuels, for example,
coals, natural gas, and petrol. Therefore, hydrogen is also
considered as a kind of “green” and sustainable energy. Besides,
hydrogen gas is a kind of efficient reductant for some
unsaturated chemicals,4−6 as well as liquid hydrogen that acts
as a combustion propellant for partial aircrafts.7 That is to say,
hydrogen gas plays a vital role in modern industry and daily
life. However, hydrogen does not occur naturally, and it has to
be processed with different methods. The big challenge is the
large-scale production of hydrogen in a sustainable way.
Nowadays, commercial hydrogen gas is generally provided by
high-temperature reformation of nonrenewable resources, such
as coal, natural gas, and petroleum.8−10 Other methods for
hydrogen production include electrolysis of water, decom-
position or hydrolysis of hydrogen-containing materials
(amine, hydrides, etc.), solar-driven photocatalytic hydrogen
production, and biohydrogen production.11−16 Among those
routes mentioned above, catalytic hydrolysis of hydrogen-
containing materials including metal hydrides (NaBH4 and
route for hydrogen production.17−19
Especially, sodium borohydride (NaBH4) is viewed as a
good candidate for hydrogen storage and generation through a
hydrolysis reaction due to its good hydrogen storage capacities
(up to 10.8 wt % in gravimetric density), nonflammable
property, and excellent resistance to alkaline solution without
any catalyst.20 Despite the fact that excellent resistance to
alkaline solution is required for the daily storage of NaBH4,
one expects rapid production of hydrogen from NaBH4
hydrolysis for actual applications, especially including hydro-
gen fuel cell vehicles. As a result, appropriate catalysts are
utilized to catalyze the hydrolysis of NaBH4 alkaline solution
controllably emitting pure hydrogen. Moreover, sodium
metaborate, as the only byproduct, is water-soluble and
environmentally benign.21 Most importantly, NaBH4 hydrol-
ysis is very rapid in the presence of favorable catalysts without
Received: December 15, 2019
Accepted: January 31, 2020
Published: January 31, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.9b22645

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external heat. Thereupon, exploring efficient catalysts for the
NaBH4 hydrolysis is an important aspect for applying the
NaBH4 hydrolysis system in the field of clean energy. Noble
metals such as Pd,22,23 Ru,24−26 Pt,27 Rh,28 and Ru−Pd−Pt
supported on varied supports29 have been testified to possess
excellent activity for hydrogen production; whereas, to some
extent, their high cost and limited reserve restrain the large-
scale applications. To address this issue, chemists are devoted
to developing various non-noble metal-based catalysts, such as
Co3O4,30,31 Co−B,32−35 Co−P−B,36 Co−Cu−B,37 Co−Ni−
P,38 Co−Mn−B,39 Ni−Co−B,40 Ni−Ni3B,41 and Co nano-
particles,42−47 for catalyzing hydrolysis of NaBH4 alkaline
solution to produce pure hydrogen gas.
As mentioned above, some Co-based catalysts and varied
Co-containing composite materials demonstrated as good
promoters for the hydrogen generation reaction.48 Herein, we
attempted to evaluate if adding a sulfur element displays the
vital feature in the hydrogen production via the catalyzed
hydrolysis of NaBH4 alkaline solution, as induced by some
artificial and non-enzymatic cobalt-based catalysts (Scheme 1).
Scheme 1. Schematic Illustration of the Catalytic Hydrogen
Production from the Hydrolysis of NaBH4 Catalyzed by
Various Cobalt-Based Catalysts That Originated from
Different Cobalt Salts
To the best of our knowledge, this is the first report on the
effect of the added sulfur-containing salts on activity
modulation of the as-prepared cobalt-based catalysts in the
present work. Innovatively, the distinguishable effect of the
adding method of sulfur-containing salts was investigated for
the catalytic hydrogen generation.
2. EXPERIMENTAL SECTION
2.1. Reagents and Instruments. All of chemical reagents were
of analytical grade without further purification. Cobalt chloride
(purity, ≥99.0%) was purchased from Tianjin Fuchen Chemicals Co.,
Ltd. The other cobalt salts (cobalt sulfate, purity of ≥99.5%; cobalt
nitrate, purity of ≥99.0%; and cobalt acetate, purity of ≥99.5%) were
products from Chengdu Kelong Chemicals Co., Ltd.
Scanning electron microscopy (SEM) was conducted on a VEGA
3SBU instrument (Tescan Co., Brno, Czech Republic) with an XFlash
Detectorm 410-M energy-dispersive X-ray spectroscopy detector
(EDX) (Bruker AXE, Karlsruhe, Germany). Transmission electron
microscopy (TEM) determination was carried out on a JEOL JEM
1200EX (Akishima-shi, Tokyo, Japan) working at 100 kV. High-
resolution TEM (HRTEM) was obtained with an FEI Tecnai G2 F20
S-Twin (Hillsboro, OR, USA) working at 200 kV. The crystalline
phases of the as-prepared Co-based catalysts and the recycled sample
were recorded on a DX-2600 X-ray diffractometer (XRD) (Fangyuan
Intrument Co., Ltd., Dandong, P. R. China) with nickel-filtered Cu
Kα radiation (λ = 1.5417 Å, 40 kV, 25 mA) in the 2θ zone of 10°−
90°. X-ray photoelectron spectroscopy (XPS) was carried out on a
Thermo ESCALAB 250XI spectrometer (Thermo Fisher Scientific
Co., Ltd., Waltham, MA, USA).
2.2. Preparation of Various Cobalt-Based Catalysts. For the
general preparation process, an aqueous solution containing 10 g of
cobalt salt was prepared with deionized water in a 500 mL beaker.
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The basicity of the as-prepared solution was adjusted to about pH
9.0−10.0 through adding ammonia with a constant flow pump. Then,
the mixture was further stirred for another 30 min followed by the
removal of ammonia in a water bath at 85 °C. The residue was cooled
to room temperature, filtered, and consecutively washed with
deionized water and anhydrous ethanol three times. The resulting
powder was dried in a vacuum drying oven and then calcined in a
muffle furnace for 2 h at 300 °C and for another 3 h at 505 °C. The
resulting sample was ground for a relatively long time, producing the
desired cobalt-based catalysts. Resulting samples coming from varied
cobalt salts (CoSO4, CoCl2, Co(OAc)2, and Co(NO3)2) are named
Co3O4-CS, Co3O4-CC, Co3O4-CA, and Co3O4-CN, respectively. As
for those catalyst samples with the additional sulfur element stemming
from Na2SO4 and Na2S, a similar preparation procedure was adopted
except one additional operation concerning the addition of sodium
sulfate or sodium sulfide. That is, Na2SO4 or Na2S with different
proportions was mixed into the aqueous solution of cobalt salts during
the preparation process.
2.3. Hydrogen Generation Measurement. The hydrogen
generation promoted by the resulting Co3O4-based catalyst in an
alkaline solution containing NaBH4 was monitored using the water
displacement method. Typically, 0.2000 g of NaBH4 and 0.0200 g of
Co3O4-based catalyst were added into a two-neck round-bottom flask.
Hydrogen generation was triggered after adding 4 mL of 10 wt %
sodium hydroxide solution at 25 °C. The volume of hydrogen
generation was recorded at intervals of 1 min. A recycling test for the
catalyst was performed at the same concentration of NaBH4 and
NaOH.
To compare the effect of introduction time of sulfur on the
hydrogen generation activity, in this research, contrast runs involving
external addition of sulfates (Na2SO4 and Na2S) were performed in
the catalytic hydrogen production system with those non-sulfur
Co3O4-based catalysts.
3. RESULTS AND DISCUSSION
3.1. Characterizations of Various Cobalt-Based Cata-
lysts. The XRD patterns of the as-prepared Co3O4-based
Figure 1. X-ray diffraction patterns of the cobalt-based catalysts used
in the present work.
catalysts are shown in Figure 1. Almost the same XRD patterns
were observed for three Co3O4-based catalysts when cobalt
chloride, cobalt acetate, and cobalt nitrate served as the catalyst
precursors. XRD patterns of the abovementioned three
catalysts match well with the standard characteristic peaks
corresponding to cubic spinel cobalt oxide (Co3O4, JCPDS no.
42-1467) as the only phase.49 These diffraction peaks are
assigned to the (111), (220), (311), (222), (400), (422),
(511) and (440) diffraction lines of the Co3O4 phase. In the
case of the fresh sample obtained by using CoSO4 as the
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Figure 2. SEM images, TEM images, and size distribution of four cobalt-based catalysts derived from different cobalt sources. Yellow-framed SEM
images are at 10.0 K times scale. The red dot and light green-framed regions are the enlarged ones of the selected parts in dash line. Size
distribution patterns are based on the corresponding TEM images. Photographs of the fresh samples are shown as insets in the corresponding size
distribution patterns.

components in the CoSO4-derived samples, which was named

Figure 3. HRTEM image of the cobalt-based catalyst named Co3O4-
CS from CoSO4.
catalyst precursor, new peaks at 2θ = 18.7°, 26.4°, 27.3°, 37.1°
correspond to the (200), (020), (201) and (301) crystal planes
of residual CoSO4 particles (PDF#46-0004), respectively,
besides those diffraction peaks of the bulk Co3O4 phase. It is
clearly demonstrated that CoSO4 particles coexist with Co3O4
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Co3O4-CS. SEM characterizations shown in Figure 2 indicate
that the Co3O4-CS displays unique fabrication of flower-like
aggregates containing sheet slices that are gathered with some
granular particles. With regard to Co3O4-CC, Co3O4-CA, and
Co3O4-CN samples without sulfur, corresponding surface
morphologies show that these samples are porous aggregates.
Interestingly, these porous textures are composed of rod-
shaped particles or thin slices on which some light-spotted
species exist, looking like tasty “rice cookies” covered with
snow-like sugar. Distinguishable surface morphologies de-
scribed above provide us direct evidence for the key role of
sulfur-containing anions (SO42−) on the morphology control-
ling of the as-prepared Co3O4-based catalysts. In other words,
the introduction of sulfate anions dramatically induces the
surface morphology transformation of a porous structure for
sulfur-free catalysts to a flower-like one for sulfur-containing
catalysts, as shown in the inset of the first SEM pattern. This
change of surface morphology shall be one factor for the best
hydrogen generation activity of the Co3O4-CS catalyst.
Element mappings shown in Figure S1 also reveal the
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Figure 4. X-ray photoelectron spectroscopy (XPS) of Co3O4-CS. (A)
Total XPS pattern of Co3O4-CS. (B) XPS of Co 2p3/2. (C) XPS of S
2p. (D) XPS of O 1s.
Figure 5. Catalytic activities of different cobalt-based samples for the
hydrogen production. Conditions: 25 °C, catalyst: 20 mg, NaBH4:
0.20 g, NaOH solution (10 wt %): 4 mL.
additional surficial sulfur besides cobalt and oxygen elements
for the Co3O4-CS sample, which is concurrent with XRD
findings.
Figure 2 illustrates the TEM images of these samples. Rice
grain-like nanoparticles were observed for Co3O4-CS, Co3O4-
CA, and Co3O4-CN. As for the Co3O4-CC catalyst, some
hexagonal or hexagonal-like nanoparticles, which are framed
with orange solid lines and red dash lines, are found to appear
along with bulk rod-shaped particles during the preparation of
catalysts. Moreover, it was observed that each kind of Co3O4-
based catalyst is indeed aggregates of nanoparticles. In
comparison with Co3O4-CC, Co3O4-CA and Co3O4-CN, a
smaller mean size of ∼10.3 nm was observed for Co3O4-CS.
High-resolution TEM of the Co3O4-CS sample is shown in
Figure 3. The interplanar spacing of nanocrystals encircled in
orange is measured as ∼0.28 nm, corresponding to the (220)
crystal plane of cubic Co3O4 nanocrystals.50 The interplanar
spacing (∼0.43 nm) of nanoparticles encircled in red is
assigned to the (200) crystal plane of residual CoSO4 particles.
This verifies that the Co3O4-CS sample used here is indeed a
mixture of CoSO4 and Co3O4, which is in strong agreement
with the obtained structural information from XRD signals
shown in the bottom plot of Figure 1.
Chemical valences of exterior elements and the surface
chemical composition of the Co3O4-CS were determined by
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XPS (Figure 4). Figure 4A shows the full XPS spectra of the
Co3O4-CS sample. Figure S2 indicates that the binding
energies (BE) of Co 2p3/2 and Co 2p1/2 are located at
781.37 and 797.02 eV, respectively. A binding energy of the Co
2p3/2 peak of 781.37 eV is almost the same as the characteristic
BE value (781.2 eV34) of bivalent cobalt. The peaks at 784.82
and 802.72 eV can be assigned to their shake-up peaks of the
main peaks. As shown in Figure 4B, the two spin-orbit
components (Co 2p1/2 and Co 2p3/2) of Co 2p splitting peaks
qualitatively have the same chemical information, revealing
that trivalent and bivalent cobalt forms (Co3+ and Co2+)
coexist in the catalyst sample. The peak at 168.82 eV (Figure
4C) is for S 2p1/2, suggesting that the CoSO4 components
coexist in Co3O4-CS samples. Meanwhile, the BE of O 1s of
531.8 eV (Figure 4D) is assigned to the lattice oxygen of the
characteristic cobalt oxide species. XPS patterns give us the
same conclusion about the mixed structure of Co3O4-CS as
that drawn from XRD and TEM determinations.
3.2. Catalytic Performances of Varied Co-Based
Catalysts for Hydrogen Generation. In the present work,
we mainly focus on the reactivity of four cobalt-based samples
prepared from different cobalt salts toward the hydrogen
production from NaBH4 hydrolysis (Figure 5). Among these
four samples, only the Co3O4-CS sample exhibited good
activity (up to an HGR of ∼1243 mL min−1 gcat−1) for the
hydrogen release. Unfortunately, the other three samples
(Co3O4-CC, Co3O4-CA, and Co3O4-CN), which originated
from sulfur-free cobalt salts, did not work in the hydrogen
production. This undesired result must be attributed to the
formation of inactive cobalt oxide (Co3O4)51 samples for these
sulfur-free catalyst precursors. Though some previous
works30,31 reported Co3O4-catalyzed NaBH4 hydrolysis pro-
ducing H2, actually, Co−B species coming from the in situ
reduction of Co3O4 are the real catalytic form, not the initial
Co3O4.52 Based on those results described above, one of the
findings is that the obtained Co3O4-CC, Co3O4-CA, and
Co3O4-CN catalysts are fully Co3O4 components, thereby not
available promoters for the hydrogen generation from NaBH4
hydrolysis. Another notable distinguishable effect indicates that
residual cobalt sulfates existing in Co3O4-CS catalysts play a
vital role in the activity improvement. Possible reasons will be
discussed in the following section.
3.3. Effects of the Added Na2SO4 or Na2S on the
Hydrogen Generation Rate (HGR). As described above,
among four cobalt-based samples, only the Co3O4-CS sample
exhibited good activity for hydrolysis of NaBH4 solution (see
Figure 5). XRD spectra in Figure 1 indicate the existence of
CoSO4 species in Co3O4-CS besides the bulk Co3O4 phase.
We conjecture that CoSO4 shall display a positive function in
the activity improvement of the Co3O4-CS sample. This
phenomenon inspired us to seek possible reasons. Accordingly,
introducing additional sulfur from two sulfur-containing
sodium salts (Na2SO4 and Na2S) was adopted with two
kinds of adding modes, that is, during the catalyst preparation
and the catalytic hydrogen generation, respectively. Figure 6
illustrates the hydrogen production efficiency using four
cobalt-based samples wherein Na2SO4 was added during
their preparation procedure, and Figure 7 is for another case
of resulting Co-based samples with the addition of Na2S during
catalyst preparation.
The observations reveal that the added Na2SO4 indeed
remarkably optimizes the catalytic performance of previous
sulfur-free Co3O4 samples. For this type of samples, the best
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Figure 6. Effects of Na2SO4 on HGR. (A−D) Time-dependent variety of HGR for different catalysts with the addition of Na2SO4 during catalyst
preparation.

Figure 7. Effects of Na2S on HGR. (A−D) Time-dependent variety of HGR for different catalysts with the addition of Na2S during catalyst
preparation.

hydrogen generation efficiency was achieved when the as-
synthesized cobalt-based samples were added with Na2SO4 (at
a 4:2 ratio of cobalt salt to Na2SO4) serving as promoters.
Hydrogen gas with a volume of 300−450 mL was successfully
collected for 10 min at the optimal ratio of cobalt salt/Na2SO4.
Meanwhile, the maximal H2 volume for each sample tends to
its theoretic value around 15 min, showing a nearly complete
hydrolysis of NaBH 4 releasing H2. Efficient hydrogen
production is probably due to the in situ formation of
catalytically active cobalt−boron (Co−B) species.
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Combining the abovementioned phenomenon with the
experimental results elucidated in Section 3.2, it hints that the
introduction of sodium sulfate probably provides a certain
influencing mechanism for the subsequent reduction of Co3O4
to reactive Co−B species. For example, the characteristic XRD
signal shown in Figure 8B identifies the formation of Co−
B53,54 after the first run for that Co3O4-CS sample. Also, black
powders that adhered on the surface of the stirrer (see the inset
of Figure 8) affirm that the reduction of cobalt ions by NaBH4
produces ferromagnetic Co−B alloys, which provides evidence
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Figure 8. (A, B) XRD patterns and (C) TEM of the collected samples
after the first run for two kinds of selected catalysts: (A) CoCl2-made
sample mixed with Na2SO4 at a ratio of 4:1 during NaBH4 hydrolysis
and (B) CoSO4-made sample. (C) TEM and HRTEM of the recycled
samples for the CoSO4-derived catalyst after the first run. The inset is
the image of the stirrer with adhered black Co−B alloys.
from a relatively weak and broad peak centered at around 2θ =
45°.51 HRTEM shown in the inset of Figure 8C of the recycled
sample shows an interplanar distance of ∼0.187 nm, which is
assignable to the (210) crystal plane of Co−B species
(PCPDF# 3-959).55 Thus, three characterizations strongly
confirm that sodium sulfate facilitates the in situ trans-
formation of Co3O4 to active Co−B species and induces the
activity improvement of previous sulfur-free catalysts.
In the case of the addition of Na2S, noteworthily, a relatively
dominant increase in HGR was observed in comparison with
the Na2SO4-induced change in HGR. Owing to the addition of
Na2S, hydrogen release was completely achieved in the range
of 10−18 min. Therefore, in this study, Na2S is regarded as a
much better sulfur-containing additive in contrast with Na2SO4
(Figures 9A−C). Namely, hydrogen gas was much rapidly
liberated reaching 300−450 mL only in a shorter period of 5
min. Only half of the reaction time for collecting a maximal H2
volume is essential for Na2S-affected catalyst samples as
compared to those analogues with the addition of NaSO4.
Figure 9. Contrast effect of Na2S to Na2SO4 on the reactivity of those catalysts derived from sulfur-free cobalt sources. (A) CoCl2-made catalyst.
(B) Co(OAc)2-made one. (C) Co(NO3)2-made one. (D) Related values.
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Also, two kinds of extrinsic sulfur-containing salts displayed
different selectivities in accelerating hydrogen generation
reaction using three cobalt-based catalysts (Figure 9 D). For
instance, distinguishable impact on the reactivity of the Co3O4-
CC catalyst was identified between the addition of Na2S and
Na2SO4, achieving up to 5-fold difference in HGR. Note-
worthy, in our case, the catalytic hydrogen production
obtained good results under relatively mild conditions
concerning a lower temperature (25 °C) and small catalyst
usage (0.02 g), in contrast with previous works.31,34,56,57 For
example, the hydrogen generation rate of a selected sulfur-
containing cobalt-based catalyst (precursor mixture, CoSO4/
Na2S = 4:4) is ∼4425 mL·min−1·gcat−1, which is 3.6 or 4.37
times active than that of cobalt oxide with a calculated HGR of
∼1230 mL·min−1·gcat‑11 in ref 31 and ∼1013 mL·min−1·gcat−11
in ref 34 (condition: 40 °C, mcat. = 0.0117 g). Compared to
those results in Table 1 of the previous report,56 our selected
cobalt-based catalyst exhibits predominant reactivity over those
catalysts (including Ni or Co powders, Raney Ni or Co, metal
borides, and related salts) reported in this literature
(condition: 25 °C, mCat. = 0.5 g). In terms of comprehensive
evaluation, the screened catalysts in our paper are more
reactive than those reported by Shharma et al.57 In short, the
addition of Na2S and Na2SO4 remarkably improves the
hydrogen production activity of previous sulfur-free catalysts
in our work.
Dramatically, we found that only in the catalyst preparation
procedure, the addition of sulfur-containing sodium salts
obviously enhanced the reactivity of the as-synthesized Co3O4-
based catalysts (see Figures 6 and 7); whereas, adding Na2SO4
or Na2S hardly accelerates the HGR only during the catalytic
reaction system (not shown here). Herein, we make sure that
active Co−B species were gradually in situ generated during
the NaBH4 hydrolysis reaction only for those catalyst samples
during which, in the preparation process, Na2SO4 or Na2S was
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Figure 10. Effects of sulfate salts on the hydrogen generation activity of those cobalt-based samples derived from sulfur-free cobalt sources. (A)
CoCl2-derived sample. (B) Co(OAc)2-derived one, (C) Co(NO3)2-derived one. Note: sulfate salts were added during the catalyst preparation.
Figure 11. Cyclic tests and related characterizations of the CoSO4-
derived catalyst with the addition of Na2S during the sample
preparation. (A) Recycling runs. (B) XPS of S 2p of the fresh sample.
(C) Size distribution of the recycled sample after the seventh run. (D)
XPS of S 2p of the recycled sample after the seventh run. The inset of
(C) shows the size distribution of the fresh sample.
added, which was confirmed by the characteristic diffraction of
Co−B species shown in Figure 8B. As for the three sulfur-free
cobalt salts, the added Na2SO4 or Na2S first reacts with partial
cobalt salts to produce cobalt sulfate as the catalyst precursor
during the catalyst preparation and consequently the resulting
CoSO4 is converted to active Co−B during the NaBH4
hydrolysis. As an example, XRD and HRTEM in Figure S3
provide direct evidences for the formation of CoSO4 species
besides a large proportion of Co3O4 when Co(OAc)2 acts as a
raw material. However, no characteristic peak of Co−B form
was detected in the obtained XRD pattern (Figure 8A) of the
collected sample after the first run for the simply mixed
catalytic system of the CoCl2-made Co3O4 sample and
Na2SO4. According to the above phenomenon, it is found
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that the obtained Co3O4 samples that originated from sulfur-
free cobalt salts are difficultly reduced to active Co−B forms by
NaBH4 in the simply mixed system of the Co3O4 sample and
Na2SO4 (or Na2S) during the hydrolysis process of NaBH4.
On the contrary, the formation of active Co−B species by
NaBH4 driven by Na2SO4 or Na2S is successfully achieved
during the preparation procedure of the Co-based catalyst.
Herein, it is presumable that one possible reason for the
obvious activity enhancement of the resulting cobalt catalysts
from those sulfur-free cobalt sources is due to the addition of
Na2SO4 or Na2S during catalyst preparation. That is, cobalt
sulfate as the key component is partly generated from the
chemical transformation in the presence of sulfur-free cobalt
salts and Na2SO4 (or Na2S). Therefore, these desired cobalt-
based catalysts shall be CoSO4-doped Co3O4 nanoparticles,
which shall exhibit a beneficial CoSO4-driven Co−B formation
and surface morphology transformation of cobalt-base samples.
However, only during the NaBH4 catalytic hydrolysis that the
addition of Na2SO4 or Na2S probably results in a simple
physical adsorption of sulfur-bearing sodium salts on the
surface of Co3O4 nanoparticles. With respect to this type of
samples, there is no positive function similar to those catalysts
wherein Na2SO4 or Na2S was added during their preparation.
Nevertheless, this appealing phenomenon impels us to explore
attractive and real reasons for the effects of sulfur-containing
salts in the future.
3.4. Reactivity Comparison of the Cobalt-Based
Catalysts Decorated by Varied Metal Sulfates. It was
well known that metal ions could influence the enzymatic
activity of natural hydrogenases via fermentative hydrogen
production.58,59 A previous report also studied the effect of
alkali metal cations on the electrolytic hydrogen evolution,59
suggesting that the hydrogen production activity trends of
various Pt electrodes correlate with the hydration energy of the
corresponding alkali metal cations present in the electrolyte
(Li+ > Na+ > K+ > Rb+ > Cs+). Taking into account the
electron transfer process in the hydrogen release reaction
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Figure 12. EDS spectra, XRD patterns, and SEM images of the CoSO4-made catalyst sample before and after recycling tests. (A, B) EDS of the
fresh sample and the collected sample after the seventh run, respectively. (C) Co 2p3/2 XPS of the recovered sample after the seventh run. (D)
XRD patterns of recycled and fresh samples. (E, F) Surface morphologies of recycled and fresh samples, respectively. (G) Sketch maps of hydrolysis
(1) of NaBH4 by in situ formed Co−B and the inhibited NaBH4 hydrolysis (2, 3) due to the gradual formation of aerosolized and colloidal NaBO2
(marked with light gray) and Co(OH)2 (marked with navy blue).

andthe positive function of Na2SO4, we attempted to further
evaluate the dependence of HGR upon a few metal sulfates
(Figure 10) in three kinds of initially sulfur-free catalytic
systems. As for all of sulfur-free cobalt-based catalysts, almost
the same influencing trend of the added sulfate salts on HGR
was observed as follows: Na2SO4 > K2SO4 > ZnSO4 > SnSO4 >
CuSO4. Two kinds of alkali metal sulfates (Na2SO4 and
K2SO4) highly improve the HGR, which is in well line with the
previous study by Razavi-Tousi and Szpunar.60 We surmise
that the current tendency possibly be ascribed to distinguish-
able effects of various sulfates on the generation and
desorption of atomic hydrogen on the surface of the Co−B
sample followed by a recombination of atomic hydrogen with
each other, producing hydrogen gas. Relatively poor impact of
the latter three metal sulfates, for example, ZnSO4, SnSO4, and
CuSO4, is possibly a result of the formation of corresponding
metal oxides. These metal oxides could cover Co3O4 particles,
inhibiting further formation of active Co−B species, leading to
relatively lower activity than those of systems in the presence
of Na2SO4 or K2SO4.
3.5. Recycling Tests. Generally, heterogeneous catalysis
desires catalysts with recyclability. In the present work, we
selected the Co3O4-based catalyst, which the precursor is
CoSO4-Na2S (Co2+/ S2− = 1:1), to study its recyclability for
hydrogen production from NaBH4 hydrolysis. After the
9383
recycling tests, the recovered catalyst was collected and
correlated characterizations were performed (Figure 11).
Figure 11A indicates that the HGR obviously decreases
along with an increase in recycling runs. A few main reasons
must be considered. One is the loss of essential CoSO4, which
is confirmed by the declined XPS (Figure 11B for the initial
sample and Figure 11D for the collected one after the seventh
run) and EDS (Figure 12) signals of the sulfur element
assigned to the CoSO4 phase. Element mappings in the insets
of Figure 12A,B also directly depict that surficial sulfur
distribution tends to be more dispersed and declines to a low
concentration level. The downward trend in sulfur concen-
tration suggests the decreased CoSO4 concentration. Accord-
ing to a previous speculation about the function of sulfur-
containing salts, the loss of sulfur-bearing species possibly fades
the driving force for the NaBH4-promoted reduction of cobalt
ions to Co−B, leading to the decreased HGR.
In addition, Co 2p3/2 XPS shown in Figure 12C reveals that
the components on the surface of the reused sample after the
seventh run include partial colloidal Co(OH)2 species with a
BE of ∼781.6 eV.61 This change in surficial components
probably results from the oxidation of Co−B species by O2 or
air during hydrogen production reaction.62 Howbeit, the top
XRD pattern shown in Figure 12D indicates the core Co−B
phase of the recovered sample after the seventh run. Based on
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ACS Appl. Mater. Interfaces 2020, 12, 9376−9386
ACS Applied Materials & Interfaces
the respective surficial and bulk analytic characteristics
between XPS and XRD technologies, it shall be reasonable
that the abovementioned XPS evidence and XRD evidence do
not match each other. The binding energy of B 1s (∼191.4 eV
for the recycled sample) shown in the inset of Figure S4
confirms the formation of thermodynamically stable and
colloidal sodium metaborate (NaBO2) as a byproduct, which
is difficult to be reversed to useful NaBH4.63 Hence, the
surficial aerosolized and amorphous shell of the recycled
sample should be mainly composed of NaBO2 and Co(OH)2
(diagrams 2 and 3 of Figure 12G). Although the core
composition of the reused catalyst after the seventh circulation
is mainly a reactive cobalt−boron phase, a gradual decrease in
HGR was also observed in this work. Decreasing HGR is
probably ascribed to the following essential factors. The
negative one is that the surface morphology of the reused
catalyst after the seventh run appears a surficial aerosolization
transformation (see the TEM image in Figure S4 and the inset
TEM of Figure 11C), which is due to the generation of NaBO2
and Co(OH)2, blocking the contact between NaBH4 and the
inner Co−B catalyst. Figure 12G visually illustrates the contact
level between NaBH4 molecules and Co−B catalysts or
Co(OH)2 with distinguishable surficial topography at different
reaction stages. Along with the increasing cycling tests, as
shown in the third picture of Figure 12G, colloidal NaBO2
further covers catalytic Co−B species and Co(OH)2 as a
precursor64 of Co−B, resulting in a decrease in HGR. Also,
XRD patterns (Figure 12D) and SEM images (Figure 12E,F)
of fresh and reused samples reveal the generation and gradual
aggregation of amorphous Co−B active species during
hydrogen production reaction. This transformation is also
accompanied by a remarkable increase in particle size with a
mean size of ∼86.2 nm (Figure 11C) in comparison with a
smaller average size of ∼10.3 nm (the inset size distribution of
Figure 11C) of the fresh sample. This should be an additional
negative factor for the decline in HGR. As a whole, the
recycled sample underwent agglomeration and surface
aerosolization, restricting the hydrogen generation rate.
4. CONCLUSIONS
In summary, a series of cobalt-based catalysts were prepared
with different cobalt salts. It was found that only one catalyst
sample prepared from CoSO4 as the precursor was able to
accelerate the release of hydrogen gas through catalytic
hydrolysis of NaBH4. Importantly, adding Na2S and Na2SO4
during catalyst preparation dramatically prompted the hydro-
gen generation reactivity of the other non-active sulfur-free
cobalt-based catalysts, which is probably due to the Na2SO4 or
Na2S-driven generation of CoSO4 as the catalyst precursor and
the subsequent formation of active Co−B species. Moreover, a
more obvious increase in the hydrogen generation rate (HGR)
was obtained in the case of adding Na2S than that of adding
Na2SO4. Though the current work speculates possible reasons
for the positive role of sulfur-bearing salts, true causes are not
clear now. It inspires us and our colleagues to further explore
the real influencing mechanism of sulfates or sulfides on
hydrogen generation. Meanwhile, we expect that the
introduction of sulfur-containing additives is probably in
favor of the other hydrogen production systems and even
other categories of catalytic reactions.
9384
■
www.acsami.org Research Article
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.9b22645.
Element mappings of four fresh cobalt-based catalysts;
Co 2p XPS pattern of the fresh sample that was derived
from CoSO4; XRD patterns and TEM images of fresh
samples derived from Co(OAc)2 during which, in the
preparation process, Na2SO4 or Na2S was added,
respectively; TEM image and B 1s XPS pattern of the
recycled catalyst after the seventh run for that as-
prepared cobalt-based sample derived from mixed
CoSO4/Na2S raw material with a ratio of 1:1 (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Weidong Jiang − School of Chemistry and Environmental
Engineering, Sichuan University of Science & Engineering,
Zigong, Sichuan 643000, P. R. China; orcid.org/0000-
0003-1775-6456; Email: jwdxb@suse.edu.cn
Authors
Xianwen Zhang − School of Chemistry and Environmental
Engineering, Sichuan University of Science & Engineering,
Zigong, Sichuan 643000, P. R. China
Qin Zhang − School of Chemistry and Environmental
Engineering, Sichuan University of Science & Engineering,
Zigong, Sichuan 643000, P. R. China
Bin Xu − School of Chemistry and Environmental Engineering,
Sichuan University of Science & Engineering, Zigong, Sichuan
643000, P. R. China
Xiaoqiang Liu − School of Chemistry and Environmental
Engineering, Sichuan University of Science & Engineering,
Zigong, Sichuan 643000, P. R. China
Kaiming Zhang − School of Chemistry and Environmental
Engineering, Sichuan University of Science & Engineering,
Zigong, Sichuan 643000, P. R. China
Guangyin Fan − School of Chemistry and Chemical Engineering,
Sichuan Normal University, Chengdu, Sichuan 610000, P. R.
China; orcid.org/0000-0001-9334-0810
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.9b22645
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work is supported by the Key Project of Sichuan Province
Key Laboratory of Vanadium & Titanium Resource
Comprehensive Utilization (no. 2018FTSZ04) and Key
Project of Zigong Science and Technology Bureau (no.
2018YYJC20). We highly appreciate Miss Caili Xu for the
curve fitting of Co (2p) XPS spectra.
■
1
ADDITIONAL NOTE
To compare our results with previous studies, in the fourth
paragraph of Section 3.3, we preliminarily calculated two
hydrogen generation rates (∼1230 mL·min−1·gcat−1 and ∼1013
mL·min−1·gcat−1) for refs 31 and 34 by the slope of respective
fitted linear plots of hydrogen volume (mL) versus time.
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ACS Applied Materials & Interfaces
■
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