Two-dimensional metal-organic framework nanosheets for highly efficient electrocatalytic biomass 5-(hydroxymethyl)furfural (HMF) valorization

Article abstract of DOI:10.1039/d0ta07793c

To construct a green chemical synthesis system for a better future of human beings, the utilization of water as an oxygen source and electricity as the driving force for the oxygenation of biomass valorization is of great significance and essential. Here, we first investigated the possibility for 5-hydroxymethylfurfural (HMF) electrooxidation into 2,5-furandicarboxylic acid (FDCA) by Ni-based two-dimensional metal-organic frameworks (2D MOFs) as electrocatalysts. FDCA is a desirable alternative to fossil-based terephthalic acids for the production of environmentally friendly polymers. The as-prepared Co-doped 2D MOFs NiCoBDC (Ni2+, BDC = terephthalic acid) have a high FDCA yield of 99%, an excellent yield rate of 20.1 μmol cm-2 h-1 and a faradaic efficiency of 78.8% at 1.55 V vs. RHE, as performed in an electrolyte at pH 13, where the degradation of HMF was ignored. Benefitting from the accessible pores of HMF molecules, abundant exposed active sites and coupling effects between Ni and Co atoms, 2D NiCo-MOFs realized a high catalytic activity and a robust electrochemical durability. This work demonstrates 2D MOFs as promising electrocatalysts for highly efficient biomass valorization because of their porosity and rich active sites.

Full text of DOI:10.1039/d0ta07793c

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J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
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DOI: 10.1039/D0TA07793C
ARTICLE
Two-dimensional metal-organic frameworks nanosheets for highly
efficient electrocatalytic biomass 5-(hydroxymethyl)furfural (HMF)
valorization
Received 00th January 20xx,
Accepted 00th January 20xx
+a
+a
a
a
a
*a
Mengke Cai, Yawei Zhang, Yiyue Zhao, Qinglin Liu, Yinle Li and Guangqin Li
DOI: 10.1039/x0xx00000x
To construct green chemical synthesis system for future life of human beings, the utilization of water as oxygen source and
electricity as driving force for the oxygenation of biomass valorization is of great significance and essential. Here we firstly
investigate the possibility for 5-hydroxymethylfurfural (HMF) electrooxidation into 2,5-furandicarboxylic acid (FDCA) by Ni-
based two-dimensional metal-organic frameworks (2D MOFs) as electrocatalyst. FDCA is a desirable alternative to substitute
fossil-based terephthalic acids for the production of environmentally friendly polymers. The as-prepared Co-doped 2D MOFs
NiCoBDC (Ni , BDC=terephthalic acid) have a high FDCA yield of 99%, excellent yield rate of 20.1 μmol cm h-1 and 78.8%
Faradaic efficiency at 1.55V vs RHE, as performed in electrolyte of pH 13, where the degradation of HMF could be ignored.
Benefited from the accessible pores for HMF molecules, abundant exposed active sites and coupling effects between Ni and
Co atoms, the 2D NiCo-MOFs realized a high catalytic activity and robust electrochemical durability. This work demonstrates
2
+
-2
2
D MOFs as a promising electrocatalysts for highly efficient biomass valorization because of their porosity and rich active
sites.
order to obtain highly active oxygen species, not only elevated
oxygen pressure and temperature are required, but also noble
metals (for example Au, Pd and Pt) have usually served as the
Introduction
1
1,12
main catalysts.
oxidation of HMF drew a lot of attention.
Over past decades, electrochemical
Biomass, as renewable and accessible precursor for versatile
fine chemicals, exhibits promising potential to reduce the
13-17
Because
compared with aerobic oxidation, the driven force can be
adjusted by both potential applied on the anodic electrode and
electrolyte concentrations, and ambient temperatures can
serve as performed conditions. At the beginning, Grabowski et
1
-3
consumption of the state-of-the-art fossil fuel. Especially, to
produce value-added chemicals, utilizing the sustainable-
derived electricity has attracted particular attention, which
meets the demand for optimizing the energy structure of power
al. probed the ability of the electrochemical oxidation of HMF
4
-6
grid.
5-Hydroxymethylfurfural (HMF) generated by
13
by Ni(OH)
2
-covered Ni mesh, achieving a low yield of only 71%
dehydrogenation of carbohydrates, classified as one of the
biomass-derived platform molecules, can be derived into a
series of valuable chemicals.
furandicarboxylic acid (FDCA) can replace terephthalic acid in
plastic industry to construct environment-friendly furan-based
polyester with similar structure and function. Corresponding
products, such as beverage bottles, textiles and food packaging
have been produced on the market by the DuPont, BASF, DSM,
and a Faradaic efficiency (FE) of 84% into FDCA in pH 14. More
recently, transition metal compounds, such as Ni, Co, Fe, Mn
7
,8
Among them, 2,5-
17,18
19,20
21,22
23,24
based phosphides,
hydroxides,
sulfides,
borides,
oxides,
25,26
27,28
29,30
(oxy)hydroxides
and their composites,
have been demonstrated a high FDCA yield and FE. Besides, it is
believed that flow reactor could improve the electrochemical
efficiency by keeping constant substrate concentration and
21,22,31
increasing substrate contact probability.
Generally, the
8
,9
SynbiaS, Avantium and ALPLA.
reaction pathway relied on the applied potential and electrolyte
Traditionally, most of studies of generation of FDCA focused concentrations, reveled by in situ spectroscopy such as Fourier
1
0
21
on aerobic oxidation of HMF using heterogeneous catalysis. In transform infrared spectra,
surface-enhanced Raman
3
0
32
spectra and sum frequency generation vibrational spectra.
However, there are still various challenges in terms of HMF
electrooxidation into FDCA. Firstly, most of the current catalytic
conditions are performed in alkaline solution with pH 14, where
HMF will degrade into useless humins. And the reaction
kinetics and mechanism have not been clearly clarified,
especially for binary or multi-metal catalysts. More importantly,
reported catalysts for HMF oxidation usually were proved to
a
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of
Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou
10275, People’s Republic of China. E-mail: liguangqin@mail.sysu.edu.cn
3
3
5
+
Mengke Cai and Yawei Zhang are co-first author.
Electronic Supplementary Information (ESI) available: See DOI: 10.1039/x0xx0000x
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DOI: 10.1039/D0TA07793C
Fig.2 Stability tests of (a) 5 mM and (b) 10 mM of HMF in different
alkaline solutions under room temperature and ambient pressure,
without stirring during 6 h test. (c) Possible self-degradation
mechanism due to Cannizzaro reaction.
introduction, HMF is not stable in high pH solution. In the early stage
of this research, we found that the repeatability of test data was very
poor when using 20 mL of pH 14 aqueous solution with 10 mM of
HMF. Considering the lab-scale electrolysis with a dilute and small
volume HMF solution, the effect of high pH had been a key factor to
influence the stability of HMF and data accuracy. Hence, we
investigated above two effects on the stability of HMF with high
performance liquid chromatography (HPLC) analysis (Fig. S1-2). Fig. 2
showed the comparison of HMF remaining with different substrate
concentrations and pH conditions. Without stirring, the 5 and 10 mM
of HMF kept only 6.2% and 12%, where large amounts of HMF
degraded due to strong alkaline environment. We noted that the
more alkaline electrolyte, the more unstable HMF. At pH 13 for a 10
mM HMF solution, the loss became rarely negligible during 6 h. This
phenomenon is mainly attributed to the self-oxidation-reduction of
HMF, as an aromatic aldehyde without α-hydrogen atom, via
Fig.1 (a) Schematic illustration of electrocatalytic biomass HMF
valorization over 2D MOFs catalyst, (b) the comparison of HMF
and water oxidation pathways in alkaline solution.
exhibit good performance for water oxidation. In other words,
HMF electrochemical oxidation serves as competition reaction
with water oxidation in aqueous electrolyte. Thus, it is critical to
balance the ability and selectivity of oxidation. Metal-organic
frameworks (MOFs), as a promising platform coordination
compounds, have shown great advantages and potentials in the
field of electrocatalysis including synthesis diversity and pore
accessibility.3
4-42
Herein, we prepared two-dimensional (2D) MOFs nanosheets
grown on the nickel foam electrode, as the first case to explore
the feasibility for biomass HMF valorization based on 2D MOFs
2
+
(
Fig. 1a). The 2D MOFs are formed by coordination of ions (Ni
2
+
or Co ) and terephthalic acid (BDC) ligands, which are good
candidates for electrochemical water oxidation integrated with
3
5,43-46
ions doping, ligand exchange and layer exfoliation.
Our
recent works found that appropriate metals and ligands doping
can promote the formation of high valence nickel species, and
adjust the structure of d-band electron, so as to improve the
4
3
electrooxidation activity.
To optimize the competitive
reactions shown in Fig. 1b, we can take the strategy of
stabilizing the high valence of Ni ions by Co-doped to improve
the FE for HMF oxidation. Furthermore, 2D MOFs can supply
enough channels for the diffusion of biomass HMF and its
products, larger than water molecules in size.
Results and discussion
Fig.3 Scanning electron microscopy (SEM), transmission electron
microscopy (TEM) and elemental mapping images of the as-
synthesized (a-d) NiBDC-NF, (e-h) NiCoBDC-NF, (i-l) NiFeBDC-NF and
(m-p) NiMnBDC-NF.
It is noticed whether it is homogeneous catalysis, heterogeneous
catalysis or electrocatalysis for HMF oxidation, the oxidation reaction
generally relies on alkaline conditions.33,47,48 As mentioned in
2
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-
Cannizzaro reaction at high ratio of OH to HMF. This finding showed 2D morphology with a micron-level lateral dimension (Fig.
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illustrates that HMF oxidation tests should be performed at as low 3c). The 2D morphology is derived from the sDpOeIc:i1a0l.1c0ry3s9t/aDl0sTtAru0c7t7u9r3eC,
alkaline conditions as possible. As MOFs-based catalysts usually which is composed of [NiO
showed weak stability in long-term electrocatalytic process, along a axis (Fig. S5). When BDC ligands dissociate, NiBDC will form
thus here lower alkaline electrolyte pH 13 was chosen for 2D sheets with b, c axis as the plane.
6
] octahedral layer and terephthalic acid
3
4-36,43-46
49
3
5,44
After introducing partial
electrooxidation conditions of HMF.
metals doping into NiBDC, pristine 2D morphology remained, and
doped metal elements (Co, Fe, Mn) could dispersed uniformly with
Ni and O (Fig. 3e-p). To further examine the composition of doped
elements, energy-dispersive X-ray spectroscopy (EDS) was applied,
and the Ni/metal-doped ratios were 10:1 (Ni/Co), 9.5:1 (Ni/Fe) and
The synthetic processes of NiBDC-NF and binary NiMBDC-NF (M =
Co, Fe, Mn) are described in the experiment section in supporting
information, and nickel foam (NF) serves as not only current
collector, but also growth substrate for 2D MOFs nanosheets. Then
the structural characteristics were studied by X-ray diffraction (XRD).
As shown in Fig. S3a, the main peak at 10° of NiBDC was relatively
weak compared with the two main peaks of NF at 45° and 52°. When
1
0:1 (Ni/Mn) shown in Table S2. The results were close to the feed
ratio of 9:1 in the synthetic step.
The electrocatalytic performance of all specimens for HMF
removed from NF substrate, all specimens exhibited strong oxidation were studied by three-electrode setup, and pH was set at
diffraction peaks (Fig. S3b), indicating good crystallinity and partial 13 during all tests. As shown in Fig. 4a, the activity of pristine NiBDC-
doping did not change the pristine NiBDC phase. Afterwards, NF was investigated by linear sweep voltammetry (LSV). To drive a
-2
nitrogen adsorption-desorption was conducted to evaluate specific current density of 10 mA cm , the applied potential for HMF
surface area and pore size distribution (Fig. S4 and Table S1). Both oxidation was about 210 mV lower than that for water oxidation,
NiCoBDC and NiFeBDC possessed larger specific surface area and indicating that the oxidation of HMF was more favorable on the
2
+
3+
pore volume, besides adsorption-desorption hysteresis loop NiBDC-NF. More interestingly, the oxidation peak of Ni to Ni
appeared. It meant that both above specimens could provide more vanished in the presence of HMF (10 mM), usually regarded as the
accessible reaction sites and hierarchical pore environment for activation
biomass electrooxidation.
process
of
Ni-based
water
oxidation
electrocatalysts.21,27,50 The main reason was that Ni oxidation feature
might be overlaid by the current of HMF oxidation. The formation of
The morphologies of the NiBDC-NF and other doping specimens
are shown in Fig. 3, which all exhibited the same nanostructure
characteristics. NiBDC nanosheets could grow vertically and
uniformly on the NF by solvothermal strategy, exposing enough
surface and pore (Fig. 3a, b). TEM images proved that the NiBDC
3
+
the high oxidation state of Ni, in this case Ni , was consumed rapidly
to oxidize HMF and no obvious redox peak could be observed. To
compare the electrochemical surface area (ECSA), which can
characterize the active sites of the electrocatalysis, Δj at 1.42 V (vs
-1
Fig.4 (a) The LSV for the NiBDC-NF at a scan rate of 5 mV s in 0.1 M KOH without and with 10 mM HMF. (b) Corresponding change of current
density plotted against scan rates without and with 10 Mm HMF. (c) Current-time and charge-time plots during constant potential (1.55 V vs
RHE) electrolysis using NiBDC-NF. (d) HPLC chromatogram at various electrolysis times. (e) Concentrations of HMF and the oxidation products
at different electrolysis time. (f) Comparison of the HMF solution before and after electrolysis.
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RHE) was plotted with different scan rates to gain the double-layer time. Encouragingly, it was obvious that Co-doped NiBDC-NF, named
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5
1
DOI: 10.1039/D0TA07793C
capacitance (Cdl). After introducing 10 mM HMF into 0.1 M KOH, as NiCoBDC-NF, showed a comparable and superior yield rate and FE,
-2
the Cdl values increased from 2.0 to 15.2 mF cm , indicating that in contrast with other three catalysts. Moreover, the electrolysis
there were more reactive sites for HMF (Fig. 4b). Similarly, the time played a key role in catalytic performance. Consistent with
Co,Fe,Mn-doped NiBDC-NF showed the same electrocatalytic above current-time plots in Fig. 4c, total FDCA yield rate decreased
properties, as shown in Fig. S6-7. Based on above results, constant as electrolysis continued, implying that flow reactor did act as a key
potential electrolysis was conducted over pristine NiBDC-NF at 1.55 process strategy for industrialization of HMF electrooxidation. Based
V vs RHE for 4 h. As electrolysis proceeded, the current density on 4 h catalytic results, the highest yield rate of 20.1 μmol cm h (a
sharply decreased due to the consumption of HMF, while the yield of 99%) was achieved at 1.55V vs RHE, while the FE of 78.8%
transferred charge kept linear increase (Fig. 4c). Continuously was obtained. The catalytic performance was comparable with most
monitored by HPLC, the reaction process was clearly demonstrated of reported electrocatalysts performed in electrolyte with pH
-2
-1
1
4-16,23,24,27,33,52,53
with exact pathway, as shown in Fig. 4d. Using NiBDC-NF as catalyst, conditions less than 14 (Table S4).
Subsequently, the
the HMF concentration decreased while FDCA increased. And there Tafel plots were determined (Fig. 5e). The NiCoBDC-NF possessed a
-1
was no dialdehyde 2,5-diformylfuran (DFF) detected as mediates Tafel slope of 60.8 mV dec in the presence of HMF, lower than that
during the total reaction period. Unfortunately, the electrooxidation of other specimens, suggesting the superior kinetic process of Co-
of HMF could not be completed within 4 h over pristine NiBDC-NF, doped specimen for HMF electrooxidation.
showing a yield of only about 60% (Fig. 4e). The comparison of the
The stability is an important factor in evaluating the
HMF solution before and after electrolysis also proved it was an
electrocatalytic performance, especially MOF-based electrocatalysts
incomplete transformation over the NiBDC-NF at 1.55 V in 4 h (Fig.
usually perform a modest stability due to weaker coordination bond
4
f). In view of the above results, there were two highlight points. The
54,55
than ionic and covalent bond.
As shown in Fig. S11-12, NiBDC-NF
one was that FDCA is generated by NiBDC-NF catalyst, following the
route of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) rather
than the route of DFF formation. Another was that the catalytic
performance was still modest over the pristine NiBDC-NF, so it was
necessary to optimize the performance by doping engineering or
adjusting the applied potential.
and NiCoBDC-NF could maintain the original crystallinity with only a
little decrease, conducted on the potential of 1.45 and 1.55 V, and
the color of specimen images did not change into black, suggesting
both specimens exhibited superior stability compared with NiFeBDC-
NF and NiMnBDC-NF. Notably, Fe-doped specimen NiFeBDC-NF
showed poor stability even if the voltage of 1.45 V was applied,
To further verify the HMF oxidation activity of as-prepared 2D indicating that Fe-doped NiBDC was not suitable to apply in HMF
MOFs specimens, applied potential and electrolysis time were oxidation. On the contrary, to assess the durability of the best
employed to investigate the FE and FDCA yield rate (Fig. S8-10). As catalyst NiCoBDC-NF, four successive electrolysis were conducted at
shown in Fig. 5a-d and Table S3, the higher applied potential, the the constant potential of 1.55 V vs RHE. As seen in Fig. 5f, the FE and
higher FDCA yield rate, while the lower FE for these catalysts. It selectivity of HMF into FDCA could be maintained around 79% and
meant that high yield rate and FE could not be achieved at the same 95%, respectively. And the yield rate decreased to 16.4 from 20.1
Fig.5 FDCA yield rate and FE of NiBDC, NiCoBDC, NiFeBDC and NiMnBDC for (a,b) 1 h and (c,d) 4h electrolysis. (e) Tafel plots in the presence
of HMF. (f) FE, selectivity and yield rate of FDCA using NiCoBDC-NF during four successive electrolysis.
4
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Figure 6. Electronic structure characterization of NiBDC-NF and NiCoBDC-NF. (a) Ni 2p, (b) Co 2p3/2, (c) C 1s and (d) O 1s of
specimens. (e) The coordinatively unsaturated sites model for the Ni atom on the surface of NiCoBDC-NF. (f) Schematic
representation of the electronic coupling between Ni and Co in NiBDC-NF and NiCoBDC-NF.
μmol cm h with a slight attenuation. Moreover, the crystallinity of interaction between Ni2+ and bridging O2- was e -e repulsion,
-
2
-1
-
-
2
+
post NiCoBDC-NF also could maintain, and the morphology and hindering the charge transfer. After introducing Co , the unpaired
elemental distribution showed limited changes after four successive electrons in the -symmetry (t2g) d-orbital could interact with
2
-
-
-
cycle electrocatalysis (Fig. S13).
bridging O via -donation, weakening the e -e repulsion and
2
+
2+
promoting partial charge transfer from Ni to Co , as implied by the
above XPS analysis.
coupling between Ni and Co could boost the formation of high
valence nickel species, which was considered as the catalytic sites for
the oxidation of organic alcohols and aldehydes.
Moreover, the X-ray photoelectron spectroscopy (XPS) was
carried out to understand the electronic states of Co-doped
NiCoBDC-NF and pristine NiBDC-NF. It was meaningful why did Co-
doped NiBDC-NF perform better in catalytic activity. Compared with
the NiBDC, the peaks of Ni 2p3/2 and Ni 2p1/2 in the high-resolution Ni
6
1-63
These results clearly demonstrated that the
2
+
2+
5
6
6
4-66
2
6
p spectrum of the NiCoBDC shifted to a higher binding energy (Fig.
a), a shift of 0.13 and 0.1 eV, respectively. This revealed that the
Conclusions
2
+
57,58
local electronic structure of Ni was modified.
hybridization, the Co was introduced into the sites of Ni in NiBDC
crystal cell. Fig. 6b showed the XPS in the Co 2p3/2 region. Two strong
peaks at 780.78 and 782.88 eV could be assigned to Co-O
O
After the
2+
2
+
In summary, a series of 2D Ni-MOFs with metal-doped (Co, Fe,
and Co- Mn) have been successfully synthesized by solvothermal
, associated with two satellite peaks. From the structural point of method, and then firstly served as electrocatalysts for the HMF
L
W
view, the Co-O bonds involved the oxygen atoms in coordinated H
2
O
electrooxidation into FDCA in a pH 13 medium. Notably, strong
alkalinity, such as pH 14, was found to be not suitable as
electrocatalytic conditions, which accelerated the degradation
of HMF, thus overestimating the electrochemical performance.
And the Co-doped NiCoBDC-NF showed excellent activity,
selectivity and stability for the HMF electrooxidation, with a
(O
W
L
) and ligands containing oxygen (O ) such as μ-OH and carboxyl
(Fig. 6e). The C 1s spectrum (Fig. 6c) was divided into three peaks.
The peak at 284.83 eV was the standard C-C as the reference, while
the peaks at 286.23 and 288.58 eV corresponded to the C-O and
5
9
C=O. Interestingly, the peaks located at 531.33 and 532.93 eV in the
-2
-1
high FDCA yield rate of 20.1 μmol cm h , excellent yield of
9%, a faradaic efficiency of 78.8% and four successive catalytic
6
0
O 1s spectrum of NiCoBDC exhibited negative shifts, compared with
31.53 and 533.23 eV in the pristine NiBDC, as shown in Fig. 6d. Thus,
9
5
cycles at 1.55V vs RHE. It was contributed to the optimized
2
+
2-
this reflected a partial electron was transferred from Ni to O , electronic structure with Co-doped, high valence of Ni formed
which was explained well in terms of their electronic structure (Fig. easily in the 2D MOFs, which was regarded as the active sites
f). The valence electronic configuration of Ni2+ was 3d , and its - for the oxidation of aldehydes and alcohols. Our study
8
6
significantly advances research towards biomass valorization,
symmetry (t2g) d-orbital were fully occupied. Thus, the major
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and stimulates extensive exploration of 2D MOFs for 21 S. Barwe, J. Weidner, S. Cychy, D. M. Morales, SV.ieDw iAertcicklehOonfelinre,
D. Hiltrop, J. Masa, M. Muhler and W. Schuhmann, Angew.
electrocatalysis and beyond.
DOI: 10.1039/D0TA07793C
Chem., Int. Ed., 2018, 57, 11460-11464.
2
2 J. Weidner, S. Barwe, K. Sliozberg, S. Piontek, J. Masa, U. P.
Apfel and W. Schuhmann, Beilstein J. Org. Chem., 2018, 14,
Conflicts of interest
1
436-1445.
2
2
2
2
2
2
3 L. Gao, Y. Bao, S. Gan, Z. Sun, Z. Song, D. Han, F. Li and L. Niu,
ChemSusChem, 2018, 11, 2547-2553.
The authors declare no conflict of interest.
4 S. R. Kubota and K. S. Choi, ChemSusChem, 2018, 11, 2138-
2
145.
5 W.-J. Liu, L. Dang, Z. Xu, H.-Q. Yu, S. Jin and G. W. Huber, ACS
Catal., 2018, 8, 5533-5541.
Acknowledgements
6 D. J. Chadderdon, L. P. Wu, Z. A. McGraw, M. Panthani and W.
Li, ChemElectroChem, 2019, 6, 3387-3392.
7 B. J. Taitt, D.-H. Nam and K.-S. Choi, ACS Catal., 2018, 9, 660-
This work was supported by the Overseas High-level Talents
Plan of China and Guangdong Province, and the 100 Talents Plan
Foundation of Sun Yat-sen University, the Fundamental
Research Funds for the Central Universities, the Program for
Guangdong Introducing Innovative and Entrepreneurial Teams
6
70.
8 S. Li, X. Sun, Z. Yao, X. Zhong, Y. Cao, Y. Liang, Z. Wei, S. Deng,
G. Zhuang, X. Li and J. Wang, Adv. Funct. Mater., 2019, 29,
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904780.
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9 L. Gao, Z. Liu, J. Ma, L. Zhong, Z. Song, J. Xu, S. Gan, D. Han and
(2017ZT07C069), the Fundamental Research Funds for the
L. Niu, Appl. Catal., B, 2020, 261, 118235.
Central Universities, and the NSFC Projects (21821003 and 30 N. Heidary and N. Kornienko, Chem. Sci., 2020, 11, 1798-1806.
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DOI: 10.1039/D0TA07793C
Table of Contents
Co-doped 2D metal-organic frameworks (MOFs) could promote biomass
valorization, the electrooxidation of 5-(hydroxymethyl)furfural (HMF) into 2,5-
furandicarboxylic acid (FDCA), with highly efficient electrocatalytic performance
due to formation of high valence of Ni, pore accessibility and electrolyte
suitability.