Journal of Applied Electrochemistry

https://doi.org/10.1007/s10800-024-02097-w

RESEARCH ARTICLE

Catalytic performance on the water decontamination

and the water‑splitting electrolysis of new phosphite salts ­(enH2)
[M(H2O)6](HPO3)2 (M=Co, Ni and Mg)
Mohamed Akouibaa1 · Brahim El Bali2 · Morgane Poupon3 · Rachid Ouarsal1 · Mohammed Lachkar1 ·
Joris More‑chevalier3 · Jan Pokorny3 · Václav Eigner3 · Michal Dusek3 · Mark D. Symes4 · Zeliha Ertekin4,5

Received: 2 October 2023 / Accepted: 3 February 2024

© The Author(s), under exclusive licence to Springer Nature B.V. 2024

Abstract
Three new organic–inorganic hybrid phosphites salts, namely, (­ enH2)[M(H2O)6](HPO3)2, with [M = Co (1), Ni (2) and Mg
(3), and “en” refers to ethylenediamine C
­ 2N2H8] have been synthesized at room temperature by the slow evaporation method.
The solid-state structures were solved from single crystal X-ray diffraction data. These compounds are isostructural, all
crystallizing in the orthorhombic system, space group, Pbca (no 61). The FTIR spectroscopy shows the expected bands of
ethylenediamine (en), water molecules, and hydrogen-phosphite oxoanion groups. The thermal stability until 100 °C of the
three compounds was confirmed using combined analyses (TGA/DTA, powder X-ray diffraction and Raman spectroscopy).
Two catalytic activity performances were investigated: the catalytic efficiency on the water decontamination of the three
compounds by the reduction of three nitrophenol isomers and the Hydrogen Evolution Reaction (HER) in an alkaline environ-
ment. The three hybrid compounds turned out to be very efficient new catalysts for reducing the three nitrophenol isomers.
The fastest electron transport and the most favorable HER reaction kinetics are displayed by (­ enH2)[Ni(H2O)6](HPO3)2, while
the highest current density with the lowest overpotential was obtained for ­(enH2)[Co(H2O)6](HPO3)2.

* Brahim El Bali
[email protected]
1
Engineering Laboratory of Organometallic, Molecular
Materials, and Environment (LIMOME), Faculty
of Sciences, University Sidi Mohamed Ben Abdellah,
30000 Fez, Morocco
2
Marrakech, Morocco
3
Institute of Physics of the Czech Academy of Sciences, Na
Slovance 2, 182 21 Prague 8, Czech Republic
4
WestCHEM, School of Chemistry, University of Glasgow,
Glasgow G12 8QQ, UK
5
Department of Chemistry, Faculty of Science, Hacettepe
University, Beytepe, 06800 Ankara, Turkey

Vol.:(0123456789)
 Journal of Applied Electrochemistry

Graphical abstract

Keywords Hybrid phosphite · X-Ray crystal structure · FTIR · Thermal analysis · Water decontamination · Water-splitting
electrode

1 Introduction present the possibility of exploring the interplay of structural

dynamics, and magnetism [5]. More recently, the synthesis
Over the past few decades, transition metal phosphates, of open-framework metal phosphites by incorporating the
exhibiting open structures, have been intensively investi- pseudo pyramidal phosphite, ­HPO3 groups, has been inves-
gated due to their rich structural chemistry and interesting tigated as a possible replacement for the traditional phos-
applications in many fields such as catalysis, chemical sepa- phate tetrahedra H ­ PO4 with great success [6–10]. Bonavia
ration, and ion-exchange processes [1–4]. Moreover, they et al. reported the first organically templated phosphite with
Journal of Applied Electrochemistry

an open framework [11], research in this area continues to structure, spectroscopic characterizations and thermal anal-
progress and a large group of eye-catching metal phosphites ysis of three isostructural hybrid phosphites, i.e., ­(enH2)
with extra-large pore openings have been isolated and char- [Co(H2O)6](HPO3)2 (1), ­(enH2)[Ni(H2O)6](HPO3)2 (2) and
acterized [12–17]. Inorganic–organic phosphite compounds ­(enH2)[Mg(H2O)6](HPO3)2 (3). Thermal stability was per-
with open-framework-based structures are emerging as an formed to identify the temperature of their decomposition.
important family [18–21]. Our research group has been They were tested as catalysts in the reduction of three nitro-
engaged in the synthesis and investigation of both simple phenol isomers (4-NP, 3-NP, and 2-NP) to their correspond-
and mixed phosphites [22–36], The structural chemistry of ing aminophenol isomers (4-AP, 3-AP, and 2-AP) and for
phosphite with ethylenediammonium cations as a structure- their potential application as Hydrogen Evolution Reaction
directing agent in the metal phosphite system has led to novel (HER) in an alkaline environment. Part of the results of the
compounds, Manganese(II) phosphate, Manganese(II) phos- present study is reported as supplementary materials.
phite, Manganese(II) phosphite oxalate, hydroxy iron(III)
phosphate, vanadium(III) phosphite, iron(III) phosphite and
cobalt(II) phosphite [37–43]. To determine the role of the
template agents in the structure, we decided to investigate 2 Experimental
three novel systems, cobalt (II), Nickel (II), and magnesium
(II) phosphite, by exploiting the templating influence of the 2.1 Synthesis
ethylenediammonium cation. The ethylenediamine (en) is a
very basic serving as a complex-forming monodentate [44], 2.1.1 (enH2)[Co(H2O)6](HPO3)2 (1)
bidentate [45, 46] ligand, or eventually being free (not coor-
dinating) in the structure [47]. Complex (1) was synthesized in ambient conditions with the
Aminophenols are important chemical compounds in presence of ethylenediamine as structure structure-direct-
synthesizing metal-complex dyes and are also used in hair- ing agent. A reaction mixture of C ­ oCl2⋅6H2O (0.4758 g,
dying agents, corrosion inhibition, and polymer production 2 mmol), ­H3PO3 (0.12 g, 1.5 mmol) and ethylenediamine
[48]. To our knowledge, only few investigations have been (0.88 g, 14.6 mmol) in 30 mL of distilled water to form a
reported on the use of hybrid organic–inorganic materials mixture in a 1:0.8:7.3 molar ratio. The synthesis was stirred
as catalysts for their reduction. In fact, industrial produc- under ambient conditions. The resulting solution, with a pH
tion of pharmaceutical analgesics such as acetaminophen of 6.5, was stirred for 4 h. After three days, well-formed
or paracetamol, the reduction of para-nitrophenol to para- good crystals were recovered, they were filtered out and
aminophenol is an important step [49]. The first step of this washed with ethanol–water (80–20%) and dried at ambient
production requires the use of a catalyst because the reduc- conditions.
tion does not occur spontaneously. In fact previous research-
ers reported on the use of different materials for the purpose,
such as hybrid organic–inorganic materials [50–53] and clay 2.1.2 (enH2)[Ni(H2O)6](HPO3)2 (2)
minerals [54]. Furthermore, studies have been done on metal
oxides and composite materials for de-colorization purposes Compound (2) was synthesized in ambient conditions with
[55, 56]. Due to their diverse utilizations, it will be inter- the presence of ethylenediamine as structure structure-
esting to find a good and inexpensive catalyst that can be directing agent. A reaction mixture of Ni(OAc) 2.4H2O
utilized in developing efficient processes for the preparation (0.04977 g, 0.2 mmol), ­H3PO3 (0.0369 g, 0.45 mmol) and
of aminophenols. ethylenediamine (0.09015 g, 1.5 mmol) in 15 mL of distilled
Electrochemical water splitting is the most promising water to form a mixture in a 1:2.3:7.5 molar ratio. The syn-
process to produce carbon–neutral hydrogen as an energy thesis was stirred under ambient conditions. The resulting
carrier, and hydrogen evolution reaction (HER) electrocata- solution, with a pH of 5.5, was stirred for 3 h. After three
lysts are essential to reduce the energy barrier and improve weeks, small hexagonal crystallites appeared, they were
the production’s efficiency. This driving force necessitates filtered out and washed with ethanol–water (80–20%) and
the design of low-cost, high-abundance, highly active, and dried at ambient conditions.
stable HER electrocatalysts [57–59].
This study aimed to synthesize new hybrid phosphite
materials with novel architecture, employing organic 2.1.3 (enH2)[Mg(H2O)6](HPO3)2 (3)
diamines as a structure-directing agent and study their
catalytic performance on water decontamination and the Compound (3) was synthesized in ambient conditions
Hydrogen Evolution Reaction (HER) in an alkaline environ- with the presence of ethylenediamine as structure struc-
ment. In this context, herein we report the synthesis, crystal ture-directing agent. A reaction mixture of ­MgCl2⋅4H2O
 Journal of Applied Electrochemistry

(0.1524 g, 0.75 mmol), H ­ 3PO3 (0.246 g, 3 mmol) and eth- The temperature ranged from 30 °C to 505 °C for 2θ range
ylenediamine (0.30 g, 5 mmol) in 25 mL of distilled water between 2 to 90° with a speed of 0.2°/s and step width of
to form a mixture in a 1:4:6.7 molar ratio. The synthesis 0.02°.
was stirred under ambient conditions. The resulting solution,
with a pH of 6.5, was stirred for 4 h. After a few days, large 2.2.4 High‑temperature Raman spectroscopy
single crystals in the form of prisms appeared, they were
filtered out and washed with ethanol–water (80–20%) and Raman spectra were recorded in the back-scattering con-
dried at ambient conditions. figuration using a Renishaw Raman spectrometer (System
1000) equipped with Bragg filters, and a 514 nm Argon
2.2 Characterizations laser. The used measurement conditions were: accumula-
tion time 200 s, laser power ca. 10 mW, at a spot size of
2.2.1 Infrared spectroscopy and thermal analysis 5 μm, (× 20, NA = 0.35, Olympus microscope objective).
The spectrometer was calibrated using the silicon F1g peak
Infrared spectra were recorded on a VERTEX 70 FTIR at 520.2 ­cm−1. Laser parallel-polarization (VV) was used to
spectrometer in the range 400–4000 ­cm−1 using the ATR measure phonon modes from 15 ­cm−1 to 4000 ­cm−1 Raman
technique at 4 ­cm−1 resolutions. shift range. The temperature measurements were performed
in a temperature chamber Linkam HFS600E-PB4 stage at
2.2.2 Determination of the crystal structures room temperature and 100 °C for each sample.

Suitable crystals were selected for Single crystal X-ray dif- 2.2.5 Thermal analysis
fraction (SCXRD) analysis. Data were collected at 120 K,
RT, and 95 K, respectively, for 1, 2 and 3, with an Oxford Thermogravimetric analysis (TGA) and differential thermal
diffraction CCD diffractometer Gemini using graphite- analyses (DTA) data were recorded on a Perkin-Elmer ana-
monochromated ­MoKα radiation (λ = 0.7173 Å), registered lyzer. The temperature varied from 25° to 600 °C at a heat-
with an Atlas S2 CCD area detector. Data were processed ing rate of 10 °C/min. Measurements were carried out on
with the program CrysAlisPro [60]. The structure solution samples in open platinum crucibles under airflow.
was solved by direct methods using Superflip [61, 62], and
the structure was refined with Jana2020 [63]. All hydro- 2.2.6 Procedure for the reduction of nitrophenol isomers
gen atoms were discernible in a difference Fourier map and
could be refined to reasonable geometry. According to com- The catalytic activity of the three complexes 1, 2 and 3 was
mon practice, H atoms bonded to C were kept in ideal posi- tested in the reduction of three nitrophenol isomers (4-NP,
tions with C–H=0.96 Å while positions of H atoms bonded 3-NP, and 2-NP) (40 mL of 4 × ­10−4 M) using sodium tet-
to N and O were refined with restrained bond lengths and H rahydroborate ­NaBH4 (40 mL of 8 × ­10−4 M). A dark yel-
atoms bonded to P were refined freely. In all cases, ­Uiso(H) low color appears due to the formation of the nitropheno-
was set to 1.2Ueq(C, N,O, P). All non-hydrogen atoms were late ion after starting the reaction without a catalyst. At the
refined using harmonic refinement.. The structural graphics same time, absorption peaks were observed at 401, 393,
were created using the software Diamond [64]. Details of and 415 nm for the para-nitrophenol, meta-nitrophenol, and
the data collection and refinements of the three structures are ortho-nitrophenol, respectively. The three catalysts 1, 2 and
given in Table X1 on supplementary material. Table X2 and 3 (each 0.05 g) were then added to the aqueous solution
X3 on supplementary material contains a selection of bond under stirring. The disappearance of the dark yellow color
distances and angles. The CIF has been deposited with the of the solution under the effect of the catalyst was followed
Cambridge Structure Database with the following CCDC by a UV–vis spectrophotometer.
codes #: 2220096 (1), 2220095 (2), and 2220094 (3).
2.2.7 Electrode preparation
2.2.3 High‑temperature X‑ray powder diffraction study
The glassy carbon (GC) electrode (BASi, d = 3.0 mm,
Powder diffraction was performed on a Rigaku Smartlab A = 0.071 ­cm2) was polished using a 0.05 μm alumina
equipped with a high-temperature chamber Anton-Paar suspension (BASi) on an alumina polishing pad, and then
HTK 1200N in Bragg–Brentano geometry using Cu Kα washed with distilled water. Cyclic voltammetry from + 1
radiation, λ = 1.54051 Å, and detector Hypix-3000 in 2D to − 1.2 V for 30 cycles at a scan rate of 100 mV/s was per-
mode scan. The temperature was increased by 5 °C/min and formed to clean the GC surface. The electrocatalyst inks
powder diffraction patterns were measured at every 30 °C.
Journal of Applied Electrochemistry

(made with compounds 1, 2 and 3, respectively) were pre- 3 Results and discussion
pared in isopropyl alcohol (IPA). The inks consisted of the
relevant catalyst (4 mg), 5% Nafion solution (50 μL) and 3.1 Crystal structure analysis
IPA (125 μL). The prepared inks were sonicated for 30 min
to obtain a homogeneous mixture, and then 5 µl of a given 3.1.1 Single crystal X‑ray diffraction
ink was drop-cast onto the GC electrode surface. The GC
electrode was dried in a vacuum desiccator for 1 h. Compounds 1, 2 and 3 are isostructural and crystallized in
the orthorhombic space group, Pbca, Z = 4. The asymmetric
2.2.8 Electrochemical measurements unit consists of a single crystallographic position of metal
M (Co, Ni, Mg) with three water molecules coordinating
The electrochemical performance of the prepared GC elec- M, ­(HPO3)2− anion and one half protonated ethylenediam-
trodes was carried out using a Gamry (Interface 1010E) monium cation (Fig. 1).
potentiostat/galvanostat in a three-electrode set-up with The 3D crystal structure corresponds to the stacking
1 M KOH as the electrolyte solution. GC electrodes modi- of ­[HPO3]2− polyhedron layers and a layer of alternate of
fied with different catalysts (compounds 1, 2 and 3) were [M(H2O)6]2+ and cations ­(H2en)2+ all connected through a
used as the working electrode with an Ag/AgCl reference large H-Bonds network (Fig. 2 and Table X3 on supplemen-
electrode (BASi, 3.0 M NaCl) and a Pt wire as the counter tary material).
electrode. The potentials versus Ag/AgCl were converted to M2+ (Co, Ni and Mg) ion is coordinated by six water mol-
that of the reversible hydrogen electrode E (RHE) using the ecules adopting a regular octahedron [M(H2O)6]. The M–O
Nernst equation: bonds are in the range of 2.0560(8)–2.0982(9) Å, 2.0338
(12)–2.0604(13) Å and 2.0420(15)–2.0742(16) Å, respec-
ERHE = E0Ag/AgCl + EAg/AgCl + 0.059pH tively for 1, 2, and 3. The cis and trans bond angles are in
the ranges of [88.62(3)–91.36(3) and 85.78(3)–94.21(3)°]
where ­E0Ag/AgCl is 0.092 V and the pH was –13.85 at 25 °C
for 1 and in [88.01(7)–91.99(4) and 86.82(7)–93.18(7)]
[65] Linear sweep voltammetry (LSV) with a scan rate of
for 2 and [89.09(5)–90.91(5) and 86.63(5)–93.37(5)°] for
5 mV/s was carried out in 1 M KOH electrolyte at room
3. These values are of the same magnitude as the ones
temperature. Each measurement was recorded after degas-
reported for ­(C 2H 10N 2)[Ni(H 2O) 6](HPO 4) 2, ­( C 2H 10N 2)
sing with nitrogen for 10 min. The LSV curves, where the
[Co(H2O)6](HPO4)2 and (­ NH4)[Mg(H2O)6](PO4), [66–68].
logarithm of the current density (mA/cm2) is plotted against
The shortest M–M distance is 7.414 Å for 1, 7.423(0) Å
the overpotential (V vs RHE), were used to derive the Tafel
for 2 and 7.427 Å for 3, which are comparable with the
slopes.
structure ­(C2H10N2)[Ni(H2O)6](HPO4)2 (7.389 Å) [66] and
­(C2H10N2)[Co(H2O)6](HPO4)2 (7.409(2) Å) [67] whose are
the corresponding phosphate structure. Within the hydrogen-
phosphite group, the P atom is in its low oxidation state
(+ III) and ­(HPO3)2− possesses a trigonal pyramidal geom-
etry. This tetrahedron exhibits three P-O distances and a
shorter bond corresponding to the P–H bond. In 1, the P–O
distances are in the range of 1.5222(8)–1.5317(8) Å, and
d(P–H)=1.356(13) Å. In 2, the P–O and P–H bond distances
range from 1.5227 (11) to 1.5335 (11) Å and d(P–H)=1.314
(17) Å. In 3, the P–O and P–H bond distances range from
1.5170(13) to 1.5261(13) and d(P–H)=1.353(17) Å. These
values lie in the same range as the ones previously reported
in the structures of ­(C 2H 10N 2)[Mn 3(HPO 3) 4] [38] and
­(C2H10N2)0.5[M(HPO3)2], with (M = V and Fe) [41].
In the three isostructural compounds, the ethylenediam-
monium organic part in the structure shows that the distance
d(C–N) and d(C–C) varies from 1.4800 (14) Å to 1.487 (2)
Fig. 1  Thermal ellipsoid, plotted at 50%, showing the asymmetric
unit for 1 (M=Co), 2 (M=Ni) and 3 (M=Mg) Å and from 1.501(3) Å to 1.5239(16) Å respectively [43,
 Journal of Applied Electrochemistry

Fig. 2  Projection along (101)-axis of the crystal structure of ­(enH2)[M(H2O)6](HPO3)2, M = Co (1), Ni (2) and Mg (3) with hydrogen bond in
light green dotted line

66, 67]. The values of the angles are equivalent to those

found for ­sp3 hybridization. This organic molecule is bonded
by moderate hydrogen bonds [69] with the phosphite group
­HPO32− (Fig. 3 and Table X2 on supplementary material).
The supramolecular three-dimensional hydrogen bonding
network is based on the oxygens of the group ­HPO32−. Each
of them are involved with two [M(H2O)6] and one [­ enH2]
cation, only the P–H bond is not involved which is the dif-
ference with the phosphate structure (­ C2H10N2)[M(H2O)6]
(HPO4)2 (M=Ni, Co) [66, 67]. The H-Bond connected to
­[enH2] cation (around 2.8 Å) has a slightly longer H-Bond
than the one involved with [M(H2O) 6] (around 2.7 Å)
(Table X2 on supplementary material) which may corre-
spond to a less energetic interaction.

3.1.2 Infrared spectroscopy

The designated infrared bands for the isostructural com-

pounds 1, 2 and 3 are listed in Table 1 and are depicted
Fig. 3  Zoom on main hydrogen bonds contacts in the structures of in Figs. 4a–c. The ethylenediammonium cation ­(C2N2H10),
­(enH2)[M(H2O)6](HPO3)2 (M=Co, Ni and Mg) with hydrogen bond
hydrogenophosphite oxyanion ­(HPO 3 ) 2− , and water
light green dotted line
Journal of Applied Electrochemistry

Table 1  Infrared bands and assignments for the three compounds

Assignment Bands ­(cm−1) ­(enH2)[Co(H2O)6] Bands ­(cm−1) ­(enH2)[Ni(H2O)6] Bands ­(cm−1) ­(enH2)
(HPO3)2 (HPO3)2 [Mg(H2O)6](HPO3)2

Asymmetric N–H bending 3280 3303 3382 and 3213

Symmetric N–H stretching 3033 3015 and 2935 3049 and 3084
Symmetric O–H stretching of water 3175 3275 3174
Symmetric stretching ­CH2 and ­NH2 2926, 2844 and 2582, 2510 3935, 2846 and 2582, 2502 2939, 2842 and 2582, 2513
­ H3+
Stretching of N 2738 and 2662 2742 and 2662 2738 and 2663
Symmetric stretching P–H 2396 and 2334 2416 and 1333 2399 and 2333
O–H Deformation of water molecule 1654 1650 1652
Bending of ­(NH3)+ 1554 and 1546 1564 1548
δas(–CH2) 1479 1479 1479
C-N 1373 1377 1371
N–H deformation of ­(NH3)+ 1149 1150 1143
Stretching vibrations P
­ O3 1052 and 972 1066 and 970 1062 and 972
Asymmetric stretching of (–C–C) 1036 and 1010 1035 and 1013 1037 and 1014
Symmetric deformation of ­PO3 658 657 672
–NH 848 850 835
NH2 rocking 718 711 721
Ni–O stretching 557 553 557

molecules as observed in the SCXRD analysis. There are results are similar to those found in the literature for
two significant bands present in the FT-IR spectrum, with other ethylenediammonium phases [21]. The symmet-
wavelengths between 3300–2300 ­cm−1 and 2334–550 ­cm−1. ric and asymmetric stretching modes of υ(–CH2–), and
The deconvolution technique offers a thorough band-based the symmetric and asymmetric deformation vibrations
interpretation. In line with the structure determined by sin- of δ(–CH 2–) are observed in the regions 2972–2620 and
gle crystal X-ray structure, the FT-IR spectrum does in fact 1515–1465 ­c m−1 respectively. The vibrational modes at
show that the molecule contains all of the functional groups. 1630 and 3440 ­c m−1 are assigned to the symmetric and
Even if it is challenging to assign each band in detail, the asymmetric vibrations of the water molecule.
most crucial attribution mode is obtained by comparison
with comparable and related chemicals that have been pub- 3.2 Thermal stability analysis
lished in the literature [50, 52, 55, 70, 71].
In these infrared spectra, the band appearing at 3.2.1 TGA, DTA and PXRD‑VD
2333 ­c m −1 corresponds to the stretching vibrations of
the υ(P–H), whereas its bending mode δ(P–H) appears The thermal stability of the three isostructural compounds
at 1036 ­c m −1. The symmetric and asymmetric stretch- was studied using thermogravimetric analysis (TGA) and
ing vibrations of the ­( PO 3 ) group are located in 1065 differential thermal analysis (DTA) under air atmosphere.
and 1145 ­c m −1 , respectively. Furthermore, we notice To understand the phase transition, the powder x-ray dif-
the symmetric deformation vibrations of the ­(PO 3 ) fraction pattern as a function of the temperature (PXRD-VD)
group at 658 ­c m −1 , while the asymmetric modes are was performed in the same condition. Before starting the
observed at 459 ­c m −1. In the cases of title complexes, experimentation as a function of the temperature, the whole
the symmetric and asymmetric stretching of (­ NH 3 ) + powder profile of the three compounds has been fitted using
are observed in the 2742 and 2662 ­c m −1. The bands at the Le Bail method using Jana2020 software [63]. The single
1154 and 1146 ­c m −1 can be related to the symmetric crystal structure determine previously in this paper was use
and asymmetric deformation of ­(NH 3)+, while its bend- to index powder diffraction patterns (Figure X1 in the sup-
ing mode appeared at 1564 ­c m−1. The presence of these plementary material). The three compounds correspond to
bands confirms the protonated form of the ethylenedi- pure and well-crystalline phase. The three compounds have
amine and diethylenetriamine molecule [71–78]. The the same behavior, to illustrate the discussion only the Fig. 5
 Journal of Applied Electrochemistry

(a)
100

2396

1373

848
1479
90

1149
2510

1680
2184
2582
80
Transmittance (%)

1654
1738
2662

1546
3280

2844

658
70

2926

718
2334
3175

3033

557
60

50

1052

972
(enH2)[Co(H2O)6](HPO3)2
40

1036

1010
3500 3000 2500 1500 1000 500
-1
Wavenumber (cm )

(b)
100
2399

1371

1143

90
1479
2187

1321
3382

2513

835
1690
2738

2582
2842

80
2663

1652

1548
2939

478
424
Transmittance (%)

70
3213

3084
3174

672
2333

60
557
721

50

40
1062

972

(enH2)[Ni(H2O)6](HPO3)2
1014

30
1037

3600 3300 3000 2700 2400 1500 1200 900 600

-1
Wavenumber (cm )
Fig. 4  a–c FTIR spectra of the three compounds (­ enH2)[M(H2O)6](HPO3)2 with (M=Co, Ni and Mg)
Journal of Applied Electrochemistry

(c)
100

1377

850
1150
1479
90

2175
2416

1650
3303
Transmittance (%)

1564
2502
2333
80

657
2582

711
3175

459
2662
1742

553
2846
3015

70
2935

1066

970
60

1012
(enH2)[Mg(H2O)6](HPO3)2

1035
50
3600 3200 2800 2400 1600 1200 800 400
Wavelength (cm-1)

Fig. 4  (continued)

corresponding to compound 1 is used, the other (Figure X2 3.2.2 Raman spectroscopy

for compound 2 and Figure X3 for compound 3 are present
in the supplementary material. The three compounds are The Raman spectra as a function of the temperature were
thermally stable until 80 °C. Afterwards, the TGA had a performed on single crystals. The Raman spectra at room
mass loss of around 30% and the DTA presented an endo- temperature of 1, 2 and 3 are shown on the Fig. 6. The
thermic peak which corresponds to the sample melting samples have the same space group materials, and many
point. This behavior is confirmed with the PXRD-VD. At common peaks are observed between their spectra. Less
Room temperature, the diffraction pattern corresponds to a peaks are reported for ­( enH 2)Co(H2O)6(HPO3)2 than for
well-crystalline pure phase of compound 1, then, after the ­( enH 2)Ni(H 2O) 6(HPO 3) 2 and ­( enH 2)Mg(H 2O) 6(HPO 3) 2.
melting transition at 85 °C, the sample shrinks and an amor- This may be due to the difference of single crystal ori-
phous diffraction pattern with some small diffraction peaks entation during the measure, and also due to the partial
is observed. The indexation of the small diffraction peak was absorbance of the photons from the laser. The peaks of
performed using the software HighScore Plus [79] equipped Raman spectra in Fig. 1 can be decomposed into several
with the PDF4 database [80] and corresponds to the high- regions: the first region, from 15 to 400 ­c m −1 , corre-
temperature sample holder (­ Al2O3) diffraction peak signa- sponds mainly to Ni–O/Co–O and Ni-H2O/Co-H2O vibra-
ture. The calculations of the mass lost do not correspond to tion modes. The second region, from 400 to 500 ­c m −1,
sum of the lost of the six waters and the ethylenediamine. corresponds to δ s(PO 3) modes. The third region, from
It is impossible to determine using only this both technic to 650 to 930 ­c m−1, corresponds to p(NH3+, ­NH 2) + bands
determine if the mass loss of around 30% observed with the of combination vibration modes. The fourth region,
TGA corresponds to the loss of the water, the loss of the eth- from 940 to 1015 ­c m −1, corresponds to νs(PO 3) modes.
ylenediamine or part of both at the same time. To complete The fifth region, from 1030 to 1140 ­c m −1, corresponds
the analysis and the understanding of the phase transition, to ν as (PO 3 ) modes. The sixth region, from 1200 to
Raman spectroscopy as a function of the temperature was 1460 ­c m −1, corresponds to δ(–CH 2) + ρ(CH 2) + ω(CH 2)
performed. vibration modes. The seventh region, from 1600 to
1700 ­c m −1, corresponds to OH deformation from ­H 2O
modes. The eighth region, from 2000 to 2700 ­c m −1 ,
 Journal of Applied Electrochemistry

Fig. 5  On the top diffraction pattern of ­(enH2)Co(H2O)6(HPO3)2 measure at room temperature and at 85 °C, on the bottom the TGA/DTA analy-
ses with the red curve corresponding to the DTA and the black curve corresponding to the TGA​

Fig. 7  Fit peaks of Raman spectra of (­enH2)[Ni(H2O)6](HPO3)2 at

Fig. 6  Raman spectra of (­ enH2)Co(H2O)6(HPO3)2 in black room temperature. Lorentz and Gaussian functions have been used to
full line, (­enH2)Ni(H2O)6(HPO3)2 in red dash line, and (­enH2) ­ 2 of 0.9989 has
fit the profile of peaks, a coefficient of determination R
Mg(H2O)6(HPO3)2 in blue dot line at room temperature been obtained
Journal of Applied Electrochemistry

Fig. 8  Raman spectra of (­enH2)Ni(H2O)6(HPO3)2 at room temperature (black full line) and at 100 °C (red dash line) in (a). In b focus of the
Raman spectra from 0 to 2000 ­cm−1 and, in c, focus from 2000 to 4000 ­cm−1

corresponds to the bands of combination and harmon- normal modes of vibrations in P ­ O3 group with a ­D3h sym-
ics between OH, NH, and CH modes. The last region metry is given by the representation Γint = ­3A1’ + 4E’ + ­A1’
(ninth one), from 2800 to 3500 ­c m -1 , corresponds to ’ + ­3A2’’ + 3E’’, for the ­C2N2H10 with ­C2h symmetry is Γint
νOH 2 + νNH 3+ + νNH 2 + νCH 2 modes. All modes were = ­11Ag + ­7Bg + ­8Au’’ + ­10Bu, and the Metal(H2O)6 has O ­ h
assigned following the references [71, 81–85] (Table 4X symmetry [81, 83–85].
on supplementary material). The compound 1 and 2 present at room temperature the
The obtained Raman spectra have been curve-fitted, same Raman spectra. However, in the case of the com-
Fig. 7 shows the fit of ­(enH2)Ni(H2O)6(HPO3)2 phase the pound ­(enH2)Co(H2O)6(HPO3)2 (1), no modes are detected
other fits are shown in supplementary materials (Figure X5, at 100 °C. After the phase transition, the material seems to
X6, X7, and X8) with Table 4X on supplementary material absorb the laser wavelength energy due to changes in the
which presents the fit results with the peak center positions material band gap. Therefore, the data from compound 2
and the optical phonon mode assignments. The number of is used to describe the phase transition. Figure 8 shows the
 Journal of Applied Electrochemistry

(a)
3,0
0min 3.0 4-NP ion
2,5 4-NP ion 0min
30sec
2.5 4-AP 30sec
1min
4-AP 2min
Absorbance

2min
2,0

Absorbance
2.0 4min
4min 6min
10min
1,5 8min
1.5
10min
1,0
1.0

0,5 0.5

0,0 0.0
250 300 350 400 450 500 550 250 300 350 400 450 500 550

(b) 0.75
1,0
0min

0,8 30sec
0min
Absorbance

0.50

Absorbance
30sec
3-AP
0,6

3-NP ion
0,4 3-AP
3-NP ion 0.25

0,2

0,0 0.00
300 350 400 450 500 550 300 350 400 450 500 550

(c)
1.25
1,4 0min 0min
30sec
1,2 30sec
1.00 2-NP ion 1min
2min
Absorbance

1min
1,0 4min
Absorbance

2-NP ion
0.75
0,8 2-AP
2-AP
0,6 0.50

0,4
0.25
0,2

0,0 0.00
300 350 400 450 500 550 300 350 400 450 500 550
Wavelength (nm) Wavelength (nm)

Fig. 9  a–c UV–visible spectra of the reduction reaction solution of a 4-nitrophenol; b 3-nitrophenol and c 2-nitrophenol in the presence of
­NaBH4 at room temperature after adding (­ enH2)[M(H2O)6](HPO3)2, M=Co (1) and Ni (2)

Raman spectra of ­(enH2)Ni(H2O)6(HPO3)2 (2) at room tem- in the vibration modes in the materials after the transi-
perature and 100 °C. Figure X9, in supplementary materials, tion. Figures 8b and c show a focus from 15 to 2000 ­cm−1
presents the Raman spectra of ­(enH2)Mg(H2O)6(HPO3)2 at and a focus from 2000 to 4000 ­cm−1 of the Raman spec-
room temperature and 100 °C. Similar changes are observed tra presented in Fig. 8a. We observe in the focus from 15
Journal of Applied Electrochemistry

3,0 to 2000 ­cm−1 (Fig. 8b) a disappearance of peaks from the

0min first region and the seventh region which correspond to
2,5 the disappearance of H ­ 2O vibrations, Ni–O, and Ni–OH
4-NP ion 30sec
vibrations. These results confirm that the ­H2O molecules
Absorbance

2min disappear during the phase melting transition at –80 °C.

2,0
4min This phenomenon leads to changes in the fourth, fifth, and
6min
sixth regions which correspond to νs(PO3), νas(PO3), and
1,5 4-AP δ(–CH2) + ρ(CH2) + ω(CH2) vibration modes. The focus,
from 2000 to 4000 ­cm−1 (Fig. 8c), confirms the H­ 2O disap-
1,0 pearance through the loss of peaks in the last region, cor-
responding to the OH stretching bands from water molecules
0,5 [82].
The amorphization phase transition is due to the 30%
mass loss of the water molecule present on the hexaaqua-
0,0
metal complex M ­ [H2O]6 (with M=Ni, Co and Mg). Moreo-
250 300 350 400 450 500 550
ver, this departure seems to transform the ethylenediamine
molecules into something else and the rearrangements in
1,0 0min the other regions seem to correspond to the formation of
30sec Ni(PO3)x clusters, which modifies the vibration energy, espe-
0,8 cially in the P
­ O3 modes regions. The phase transition occurs
around 80 °C, the material should not be heated above this
Absorbance

0,6
temperature during its use or shaping.

3-AP 3.3 Catalytic activity on water decontamination

0,4
3-NP ion of nitrophenol isomers
0,2
The complexes 1, 2 and 3 were tested to investigate the
catalytic efficiency for the reduction reaction of three nitro-
0,0 phenol isomers (4-nitrophenol, 3-nitrophenol and 2-nitro-
300 350 400 450 500 550 phenol), using sodium tetrahydroborate ­NaBH4. The results
are plotted Fig. 9i–k for compounds 1 and 2 and Fig. 10i–k
1,4 for compound 3. Once the ­NaBH4 was added at the starting
0min
point, we observed a strong coloration of the solution due
1,2 30sec to the formation of the phenolate anions. However, after the
1,0 1min addition of the hybrid compound, we noticed a rapid reac-
Absorbance

2-NP ion tion, in which the solution becomes decolorated in all of the
0,8 cases. So, there is probably a formation of the aminophenol
2-AP
isomers 4-AP, 3-AP, and 2-AP. The higher peaks of absorp-
0,6
tion placed at 401, 393, and 415 nm disappear, giving rise
0,4 to new peaks situated at 317, 328, and 347 nm for the 4-NP,
3-NP, and 2-NP, respectively. 10 min, 30 s, and 4 min were
0,2 the necessary time to achieve the reaction with the appear-
ance of the three aminophenol isomers (4-AP, 3-AP, and
0,0
2-AP), at room temperature. A comparison between some
250 300 350 400 450 500 550
Wavelength (nm) previous work and our study is given in Table 2. These
results demonstrate the high catalytic efficiency of the three
prepared complexes ­(enH2)[M(H2O)6](HPO3)2 with (M=Co,
Fig. 10  a–c UV–visible spectra of the reduction reaction solution of a
4-nitrophenol; b 3-nitrophenol and c 2-nitrophenol in the presence of
Ni and Mg).
­NaBH4 at room temperature after adding (­ enH2)[Mg(H2O)6](HPO3)
 Journal of Applied Electrochemistry

Table 2  A comparison of Catalyst Type Concentration Reaction time (min) References
reaction time for the reduction of NP (mol/L)
of three nitrophenol isomers
by ­(enH2)[M(H2O)6](HPO3)2, (enH2)[Co(H2O)6](HPO3)2 ­(enH2) Hybrid-material 4 × ­10−4 10 for 4-NP This work
M=Co, Ni and Mg, compared [Mg(H2O)6](HPO3)2 0.5 for 3-NP
to known catalysts (enH2)[Ni(H2O)6](HPO3)2 4 for 2-NP
(C4H16N3)[Ni(NO3)(C2O4)2]⋅2H2O Hybrid-material 4 × ­10−4 0.5 for 4-NP [50]
0.5 for 3-NP
0.5 for 2-NP
(C4H12N2)[Co(H2O)6](HPO4)2 Hybrid-material 4 × ­10−4 4 for 4-NP [51]
0.5 for 3-NP
4 for 2-NP
(C4H16N3)[Cu(NO3)(C2O4)2]⋅2H2O Hybrid-material 4 × ­10−4 1 for 4-NP [52]
0.5 for 3-NP
1 for 2-NP
CuMoO4 Nanoparticles 4 × ­10−4 14 for 4-NP [55]
6 for 3-NP
14 for 2-NP
NiMoO4 Nanoparticles 2 × ­10−4 8 for 4-NP [86]
3 for 3-NP
8 for 2-NP

3.4 Hydrogen evolution reaction (HER) electrode 4 Conclusions

in an alkaline environment
Three new inorganic–organic hybrid phosphite compounds
In Fig. 11, electrochemical measurements of the three com- ­(enH2)[M(H2O)6](HPO3)2 (M=Co, Ni, Mg) have been syn-
pounds ­(enH2)[M(H2O)6](HPO3)2 with (M=Co (1), Ni (2) thesized at room temperature by a slow evaporation method.
and Mg (3) were performed in 1 M KOH electrolyte using a Structural analysis indicates that these compounds are iso-
typical three-electrode set-up. LSV curves without IR com- structural and possess a similar three-dimensional network,
pensation showed that glassy carbon electrodes covered by constructed from octahedra M(H2O)6 (M=Co, Ni, Mg),
these phosphate compounds had a higher current density ­HPO3 pseudo-tetrahedral and ethylenediammonium cations
compared to bare glassy carbon electrodes as illustrated in ­(H2en)2+, interacting via an intricate H–Bonds network. I.R.
Fig. 8a. Tafel plots were delivered to examine the alkaline spectroscopy confirmed the structural data, with the pres-
HER kinetics further, as shown in Fig. 8b. The Volmer reac- ence of the characteristic vibrational bands of the hydrog-
tion is the rate-determining step for HER activity accord- enophosphite oxyanion (­ HPO3)2−, ethylenediammonium
ing to the obtained Tafel slopes. The Tafel slope for 2 is cation, and the water molecules. The combined analyses
90 mV/dec, which is lower than that of 1 (182 mV/dec) and DTA/TGA, PXRD-VT and the Raman spectroscopy confirm
3 (188 mV/dec). However, none of these electrocatalysts is the degradation of the phosphite material after 80 °C due to
especially active for alkaline HER activity, with large over- the loss of the water molecule complex with the metal. After
potentials of 495, 523 and 543 mV (at a current density of this temperature, the compounds have amorphous structures.
10 mA ­cm–2) being observed for electrodes modified with The high catalytic efficiency of the three as-prepared com-
compounds 1, 2, and 3, respectively (Fig. 8c). Based on plexes has proved to be efficient and sufficient for the con-
the Tafel data, the fastest electron transport and the most version of the 4-NP, 3-NP, and 2-NP nitrophenol isomers to
favorable HER reaction kinetics are displayed by the Ni- (4-AP, 3-AP, and 2-AP) aminophenol isomers, respectively,
containing material (2). On the other hand, the highest cur- at room temperature. With large overpotentials of 495, 523,
rent density with the lowest overpotential was obtained for and 543 mV (at a current density of 10 mA ­cm–2) being
Co(II)-containing compound 1. The catalytic activity of observed for electrodes modified with compounds 1, 2, and
these compounds may be greatly influenced by their mor- 3, none of them seemed active for alkaline HER activity.
phology, which may have some bearing on their relative Based on the Tafel data, the fastest electron transport and
performance [86]. the most favorable HER reaction kinetics are displayed by
(2), while the highest current density, with the lowest over-
potential, was obtained for (1).
Journal of Applied Electrochemistry

Fig. 11  Electrochemical performance of the three compounds ­(enH2)[M(H2O)6](HPO3)2 with (M=Co (1), Ni (2) and Mg (3)) in 1 M KOH. a
LSV curves, b their corresponding Tafel plots and c overpotentials required to afford a current density of 10 mA ­cm–2

Supplementary Information The online version contains supplemen- Declarations

tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 10800-0​ 24-0​ 2097-w.
Competing interest The authors declare no competing interests.
Author contributions MA performed all the syntheses and descibed
the results, helped somewhere by RO under the supervision of ML;
MP, VE and MD performed the single crystal X-ray diffraction, JM
and JP measured the Raman spectra and TG/TDA measurements, ZE
and MDS studied the catalytic performance of the searched materials.
BEB suggested the research and validated the manuscript. References
Funding ZE thanks the Scientific and Technological Research Council 1. Davis ME (2002) Ordered porous materials for emerging applica-
of Turkey (Grant Number: TUBITAK 2219) for a postdoctoral fel- tions. Nature 417:813–821. https://​doi.​org/​10.​1038/​natur​e00785
lowship. MDS thanks the Royal Society for a University Research 2. Parnham ER, Morris RE (2007) Ionothermal synthesis of zeolites,
Fellowship (150104). This research was supported by the project metal–organic frameworks, and inorganic-organic hybrids. Acc
20-LM2023051 of the Czech Science Foundation. Chem Res 40:1005–1013. https://​doi.​org/​10.​1021/​ar700​025k
3. Jiang J, Yu J, Corma A (2010) Extra-large-pore zeolites: bridg-
ing the gap between micro and mesoporous structures. Angew
 Journal of Applied Electrochemistry

Chem Int Ed 49:3120–3145. https://​doi.​org/​10.​1002/​anie.​20090​ spectroscopic, and magnetic properties. J Solid-State Chem
4016 178:3554–3562. https://​doi.​org/​10.​1016/j.​jssc.​2005.​09.​032
4. Natarajan S, Mandal S (2008) Open-framework structures of 19. Wang KC, Bian YX, Li J, Xu DG, Lin ZE (2016) Amine-ligated
transition-metal compounds. Angew Chem Int Ed 47:4798–4828. approach for the synthesis of extra-large-pore zinc phosphites with
https://​doi.​org/​10.​1002/​anie.​20070​1404 qtz-h and bnn topologies. Inorg Chem 55:3727–3729. https://​doi.​
5. Guillou N, Gao Q, Foster PM, Chang J-S, Nogues M, Park S-E, org/​10.​1021/​acs.​inorg​chem.​6b005​89
Ferey G, Cheetham AK (2001) Nickel (II) phosphate VSB-5: a 20. Fernandez S, Mesa JL, Pizarro JL, Lezama L, Arriortua MI,
magnetic nanoporous hydrogenation catalyst with 24-ring tunnels. Olazcuaga R, Rojo T (2000) A new layered inorganic-organic
Angew Chem Int Ed 40:2831–2834. https://d​ oi.o​ rg/1​ 0.1​ 002/1​ 521-​ hybrid manganese (II) phosphite:(C2H 10N 2)[Mn 3 ­( HPO 3) 4].
3773(20010​803)​40:​15%​3c283​1::​AID-​ANIE2​831%​3e3.0.​CO;2-Z Hydrothermal synthesis, crystal structure, and spectroscopic
6. Wang P, Wang G-M, Li J-H, Wang Z-H, Wang Y-X, Lin J-H and magnetic properties. Chem Mater 12:2092–2098. https://​
(2012) Syntheses and structures of two open-framework zinc doi.​org/​10.​1021/​cm001​026s
phosphites with extra-large 24-ring channels. Solid State Sci 21. Fernandez S, Mesa JL, Pizarro JL, Lezama L, Arriortua
14:1030–1035. https://​doi.​org/​10.​1016/j.​solid​state​scien​ces.​2012.​ MI, Rojo T (2001) Hydrothermal synthesis of a new layered
05.​007 inorganic-organic hybrid cobalt (II) phosphite:(C 2 H 10 N 2 )
7. Lin H-Y, Chin C-Y, Huang H-L, Huang W-Y, Sie M-J, Huang L-H, [Co 3(HPO 3) 4]: crystal structure and spectroscopic and mag-
Lee Y-H, Lin C-H, Lii K-H, Bu X, Wang S-L (2013) Crystalline netic properties. Int J Inorg Mater 3:331–336. https://​doi.​org/​
inorganic frameworks with 56-ring, 64-ring, and 72-ring channels. 10.​1016/​S1466-​6049(01)​00031-9
Science 339:811–813. https://​doi.​org/​10.​1126/​scien​ce.​12320​97 22. Ouarsal R, Tahiri AA, El Bali B, Lachkar M, Bolte M (2002)
8. Teofilo R, Jose Luis M, Jorge L, Begona B, Pizarro JL, Isabel Strontium dihydrogenphosphite. Acta Crystallogr Sect E
Arriortuab JL (2009) Organically templated open-framework E58:i19–i20. https://​doi.​org/​10.​1107/​S1600​53680​20008​06
phosphites. J Mater Chem 19:3793–3818. https://d​ oi.o​ rg/1​ 0.1​ 039/​ 23. Ouarsal R, Tahiri AA, Lachkar M, Slimani Z, El Bali B, Bolte
B8087​95B B (2002) Barium dihydrogen phosphate hemihydrates. Acta
9. Yang Y, Zhao Y, Yu J, Wu S, Wang R (2008) Doping-induced Crystallogr Sect E E58:i72–i73. https://​doi.​org/​10.​1107/​S1600​
structure variation of 1,3-cyclohexane-bis(methylamine)-tem- 53680​20135​69
plated zinc-phosphorus open structures. Inorg Chem 47:769–771. 24. Chaouche S, Ouarsal R, El Bali B, Lachkar M, Bolte M, Dusek
https://​doi.​org/​10.​1021/​ic701​825m M (2010) L ­ i 2HPO 3 ­H 2O: crystal structure and IR spectrum.
10. Wang G-M, Li J-H, Zhang X, Jiang W-W, Bao Z-Z, Zhao X-M, J Chem Crystallogr 40:526–530. https://​d oi.​o rg/​1 0.​1 007/​
Wang Y-X, Lin J-H (2014) ­(C5H6N)4[Be6(HPO3)8]·H2O: a low- s10870-​010-​9690-1
density open-framework beryllium phosphite with multidirec- 25. El Bali B, Massa W (2002) Redetermination of copper(II)
tional 12-ring channels. Solid State Sci 33:53–57. https://​doi.​org/​ hydrogenphosphite dehydrate. Acta Crystallogr E E58:i29–i31.
10.​1016/j.​solid​state​scien​ces.​2014.​04.​013 https://​doi.​org/​10.​1107/​S1600​53680​20035​74
11. Bonavia G, De Bord J, Haushalter RC, Rose D, Zubieta J (1995) 26. Chaouch S, Ouarsal R, Akouibaa M, Rakib S, Lachkar M, El
Hydrothermal synthesis and characterization of two- and three- Bali B, Dusek M (2018) ­Cs2[M(H2O)6]3(HPO3)4, M= Co, Ni:
dimensional solids of the oxovanadium(IV)-phosphite system. the Crystal structures, IR and thermal studies. J Phys Conf Ser
structures of [HN(Me)(CH2CH2)2N(Me)H][(VO)4(OH)2(HPO3)4], 984:12–15. https://​doi.​org/​10.​1088/​1742-​6596/​984/1/​012015
­[H2N(CH2CH2)2NH2][(VO)3(HPO3)4(H2O)2], and [VO(HPO3) 27. Ouarsal R, Tahiri AA, El Bali B, Lachkar M, Harrison WTA
(H2O)]. Chem Mater 7:1995–1998. https://d​ oi.o​ rg/1​ 0.1​ 021/c​ m000​ (2002) Sodium zinc tris(dihydrogenphosphite) hydrate
59a002 NaZn(H2PO3)3⋅H2O. Acta Crystallogr E58:i23–i25. https://​doi.​
12. Zhao L, Li J, Chen P, Li G, Yu J, Xu R (2008) [­Co 8 org/​10.​1107/​S1600​53680​20022​09
­(HPO3)9(CH3OH)3]·2H2O: an open-framework cobalt phosphite 28. Ouarsal R, Tahiri AA, Lachkar M, Dusek M, Fejfarová K, El
containing extra-large 18-ring channels. Chem Mater 20:17–19. Bali B (2003) Sodium magnesium tris(dihydrogenphosphite)
https://​doi.​org/​10.​1021/​cm702​1906 monohydratehydrate, NaMg(H 2PO 3) 3⋅H 2O. Acta Crystallogr
13. Liang J, Li J, Yu J, Chen P, Li L, Xu R (2006) [Ni(C6N2H14)2] E59:i33–i35. https://​doi.​org/​10.​1107/​S1600​53680​30027​57
[Zn4 ­(H2O)(HPO3)5]: a new open-framework zinc phosphite with 29. Ouarsal R, Essehli R, Lachkar M, Zenkouar M, Dusek
intersecting 8-, 12- and 16-ring channels. J Solid-State Chem M, Fejfarová K, El Bali B (2004) Dipotassium cobalt(II)
179:1977–1983. https://​doi.​org/​10.​1016/j.​jssc.​2006.​03.​034 bis(hydrogenphosphite) dihydrate, K ­ 2Co(HPO3)2⋅2H2O. Acta
14. Chen W, Li N, Xiang S (2004) Z ­ n3(HPO3)4·Zn(H2O)6: a purely Crystallogr E60:i66–i68. https://​doi.​org/​10.​1107/​S1600​53680​
inorganic open-framework zincophosphite with octahedral zinc 40078​95
complex [Zn(H2O)6]2+ encapsulating in the channels. J Solid-State 30. Menssouri I, El Bali B, Capitelli F, Piniella JF, Lachkar M, Sli-
Chem 177:3229–3234. https://​doi.​org/​10.​1016/j.​jssc.​2004.​04.​060 mani Z (2005) Diammoniumtris[hexaaquamagnesium(II)]tetra
15. Li J, Li L, Liang J, Chen P, Yu J, Xu Y, Xu R (2008) Template- kis[hydrogenphosphate(III)], ­(NH4)2[Mg(H2O)6]3(HPO3)4. Acta
designed syntheses of open-framework zinc phosphites with extra- Crystallogr E61:i129–i131. https://​doi.​org/​10.​1107/​S1600​53680​
large 24-ring channels. Cryst Growth Des 8:2318–2323. https://​ 50172​3X
doi.​org/​10.​1021/​cg701​080u 31. Ouarsal R, El Bali B, Lachkar M, Dusek M, Fejfarova K
16. Luo X, Luo D, Zeng H, Gong M, Chen Y, Lin Z (2011) A 3,4-con- (2005) Diammoniumtris [hexaaquanickel(II)] tetrakis[hydroge
nected beryllium phosphite framework containing 24-ring chan- nphosphate(III)], ­(NH4)2[Ni(H2O)6]3(HPO3)4. Acta Crystallogr
nels with a very low density. Inorg Chem 50:8697–8699. https://​ E61:i171–i173. https://​doi.​org/​10.​1107/​S1600​53680​50217​20
doi.​org/​10.​1021/​ic201​4539 32. Ouarsal R, El Bali B, Lachkar M, Dusek M, Fejfarova k, (2005)
17. Lai Y-L, Lii K-H, Wang S-L (2007) 26-ring-channel structure Diammonium tris[hexaaquacobalt(II)] tetrakis[hydrogenph
constructed from bimetal phosphite helical chains. J Am Chem osphate(III)], ­( NH 4) 2[Co(H 2O) 6] 3(HPO 3) 4. Acta Crystallogr
Soc 129:5350–5351. https://​doi.​org/​10.​1021/​ja070​733k E61:i168–i170. https://​doi.​org/​10.​1107/​S1600​53680​50217​19
18. Fernandez S, Mesa JL, Pizarro JL, Chung U-C, Arriortua MI, 33. Ouarsal R, Lachkar M, Dusek M, Albert EB, Castelló GBC,
Rojo T (2005) Two new two-dimensional organically templated El Bali B (2016) Crystal structure of NaCd(H2PO3)3⋅H2O and
phosphite compounds:(C 6H16N2)0.5[M ­(HPO3)F], M= Fe(II) spectroscopic study of NaM(H2PO3)3⋅H2O, M = Mn Co, Ni,
and Co(II): solvothermal synthesis, crystal structures, thermal,
Journal of Applied Electrochemistry

Zn, Mg and Cd. Polyhedron 106:132–137. https://​doi.​org/​10.​ 46. Pham DNK, Roy M, Golen JA, Manke DR (2017) The first-row
1016/j.​poly.​2016.​01.​006 transition-metal series of tris (ethylenediamine) diacetate com-
34. Chaouche S, Ouarsal R, Lachkar M, Capitelli F, El Bali B (2010) plexes [M(en)3](OAc)2 (M is Mn, Fe Co, Ni, Cu, and Zn). Acta
Crystal structure and IR study of ­( C 6H 5NH 3)[ZnCl(HPO 3)]. Crystallogr C 73:442–446. https://​doi.​org/​10.​1107/​S2053​22961​
J Chem Crystallogr 40:486–490. https://​d oi.​o rg/​1 0.​1 007/​ 70067​38
s10870-​009-​9682-1 47. Dardar F, Day CS, El Jazouli A, Sebti S, Lachgar A (2019) Syn-
35. Hamdi N, Chaouch S, da Silva I, Ezahri M, Lachkar M, Alhasan thesis and characterization of a new layered gallium phosphonate
R, Yaman Abdin A, Jacob C, El Bali B (2019) Synthesis, struc- oxalate ­[C2H10N2]0.5[Ga3 ­(PO3CH3)4(C2O4)]⋅H2O. J Chem Crys-
tural characterization, and biological activities of organically tallogr 49:44–51. https://​doi.​org/​10.​1007/​s10870-​018-​00762-5
templated cobalt phosphite ­(C4N2H14)[Co(H2PO3)4]·2H2O. Sci 48. Espinosa Bosch M, Ruiz Sánchez AJ, Sánchez Rojas F, Bosch
1:41. https://​doi.​org/​10.​3390/​sci10​20041 Ojeda C (2006) Determination of paracetamol: historical evo-
36. Hamdi N, Hidaoui S, Hassani HO, Lachkar M, Dusek M, Morley lution. J Pharm Biomed 42:291–321. https://​doi.​org/​10.​1016/j.​
N, El Bali B (2020) Crystal structure, physical and catalytic oxi- jpba.​2006.​04.​007
dation studies of a new hybrid phosphate [(N2H5)2Co(HPO4)2]. J 49. Yang P, Xua A, Xiab J, Hea J, Xinga H, Zhanga X, Weia S,
Mol Struct. https://​doi.​org/​10.​1016/j.​molst​ruc.​2020.​128317 Wanga N (2014) Facile synthesis of highly catalytic activity
37. Escobal J, Pizarro JL, Mesa JL, Lezama L, Olazcuaga R, Arriortua Ni-Co-Pd-P composite for reduction of the p-Nitrophenol. Appl
MI, Rojo T (2000) A new manganese (II) phosphate templated by Catal Gen 470:89–96. https://​doi.​org/​10.​1016/j.​apcata.​2013.​10.​
ethylenediamine: ­(C2H10N2)[Mn2(HPO4)3(H2O)]. Hydrothermal 043
synthesis, crystal structure, and spectroscopic and magnetic prop- 50. Akouibaa M, Hassani HO, Ouarsal R, Rakib S, Lachkar M, Pou-
erties. Chem Mater 12:376–382. https://​doi.​org/​10.​1021/​cm991​ pon M, Dusek M, Morley N, El Bali B (2022) ­(H3dien)[Ni(NO3)
0815 (C2O4)2]⋅2H2O: synthesis, crystal structure, catalytic activity and
38. Fernández S, Mesa JL, Pizarro JL, Lezama L, Arriortua MI, magnetic study. Chem Data Collect 42:100969. https://d​ oi.o​ rg/1​ 0.​
Olazcuaga R, Rojo T (2000) A new layered inorganic-organic 1016/j.​cdc.​2022.​100969
hybrid manganese (II) phosphite: (­C 2H 10N 2)[Mn 3(HPO 3) 4]. 51. Hidaoui S, Hamdi N, Akouibaa M, Benali-Cherif R, Vaclav E,
Hydrothermal synthesis, crystal structure, and spectroscopic and Dusek M, Lachkar M, El Bali B (2022) Synthesis, crystal struc-
magnetic properties. Chem Mater 12:2092–2098. https://​doi.​org/​ ture and catalytic activity of the new hybrid phosphate (­ C4H12N2)
10.​1021/​cm001​026s [Co(H2O)6](HPO4)2. J Mol Struct 1265:133296. https://​doi.​org/​
39. Ramaswamy P, Mandal S, Natarajan S (2009) Synthesis, structure 10.​1016/j.​molst​ruc.​2022.​133296
and magnetic behavior of a new three-dimensional manganese 52. Akouibaa M, Kadiri M, Driouch M, Tanji K, Ouarsal R, Rakib S,
phosphite-oxalate: ­[C2N2H10][Mn2II(H2O)2(HPO3)2(C2O4)]. J Sfaira M, Morley N, Lachkar M, El Bali B, Zarrouk A, Bendeif
Solid-State Chem 182:2491–2496. https://​doi.​org/​10.​1016/j.​jssc.​ E (2023) Synthesis, catalytic activity, magnetic study and anti-
2009.​06.​040 corrosive activity of mild steel in HCl 1M medium of (­ H3dien)
40. Jeffrey RD, De Bord J, Reiff WM, Haushalter RC, Zubieta J [Cu(NO3)(C2O4)2]⋅2H2O. A redetermination at 100 K. Mater
(1996) The first organically templated layered iron phosphate: Chem Phys 307:128130. https://​doi.​org/​10.​1016/j.​match​emphys.​
hydrothermal synthesis, structure, magnetic properties, and the 2023.​128130
Mössbauer spectrum of ­[H3NCH2CH2NH3]0.5[Fe(OH)(PO4)]. J 53. Ramírez-Rave S, Hernández-Gordillo A, Calderón HA, Galano A,
Solid-State Chem 125:186–191. https://d​ oi.o​ rg/1​ 0.1​ 006/j​ ssc.1​ 996.​ García-Mendoza C, Gómez R (2015) Synthesis of new ZnS–Bipy
0284 based hybrid organic–inorganic materials for photocatalytic reduc-
41. Fernández S, Mesa JL, Pizarro JL, Lezama L, Arriortua MI, tion of 4-nitrophenol. New J Chem 39:2188–2194. https://d​ oi.o​ rg/​
Rojo T (2002) Two new three-dimensional vanadium (III) 10.​1039/​C4NJ0​1891E
and iron (III) phosphites templated by ethylenediamine: 54. Li N, Sun Q, Zhang P, Jing P (2021) Hydrothermal synthesis of
­(C2H10N2)0.5[M(HPO3)2]. ab initio structure determination, spec- 1T-MoS2/pelagic clay composite and its application in the cata-
troscopic, and magnetic properties. Chem Mater 14:2300–2307. lytic reduction of 4-nitrophenol. Materials 14:7020. https://​doi.​
https://​doi.​org/​10.​1021/​cm011​2845 org/​10.​3390/​ma142​27020
42. Fernández S, Mesa JL, Pizarro JL, Lezama L, Arriortua MI, Rojo 55. Hassani HO, Akouibaa M, Rakass S, Abboudi M, El Bali B,
T (2001) Hydrothermal synthesis of a new layered inorganic- Lachkar M, Al Wadaani F (2021) A simple and cost-effective new
organic hybrid cobalt (II) phosphite: ­(C2H10N2)[Co3(HPO3)4]: synthesis method of copper molybdate C ­ uMoO4 nanoparticles and
crystal structure and spectroscopic and magnetic properties. Int J their catalytic performance. J Sci Adv Mater Devices 6:501–507.
Inorg Mater 3:331–336. https://​doi.​org/​10.​1016/​S1466-​6049(01)​ https://​doi.​org/​10.​1016/j.​jsamd.​2021.​06.​003
00031-9 56. Mohamed MJS, Shenoy S, Bhat DK (2018) Novel NRGO-
43. Chung U-C, Mesa J, Pizarro J, Lezama L, Garitaonandia J, Chap- CoWO4-Fe2O3 nanocomposite as an efficient catalyst for dye
man JP, Arriortua MI (2004) A new layered organically templated degradation and reduction of 4-nitrophenol. Mater Chem Phys
iron(II) phosphite, (­ C2H10N2)Fe3(HPO3)4: hydrothermal synthe- 208:112–122. https://d​ oi.o​ rg/1​ 0.1​ 016/j.m
​ atche​ mphys.2​ 018.0​ 1.0​ 12
sis, crystal structure and spectroscopic and magnetic properties. J 57. Dedzo GK, Pameté E, Saheu MRT, Ngnie G, Nanseu-Njiki CP,
Solid-State Chem 177:2705–2713. https://​doi.​org/​10.​1016/j.​jssc.​ Detellier C, Ngameni E (2017) Hydrogen evolution reaction at
2004.​04.​020 PdNPs decorated 1:1 clay minerals and application to the elec-
44. Yeşilel OZ, Ölmez H, Arici C (2007) The first bis (orotato-N, trocatalytic determination of p-nitrophenol. J Electroanal Chem
O) cadmium complex with monodentate protonated ethylenedi- 801:49–56. https://​doi.​org/​10.​1016/j.​jelec​hem.​2017.​07.​030
amine ligands: synthesis, spectrothermal properties of a cadmium 58. Zhao H, Yuan ZY (2020) Insights into transition metal phosphate
(II)-orotato complex with ethylenediamine–crystal structure materials for efficient electrocatalysis. ChemCatChem 12:3797–
of trans-[Cd(HOr) 2(enH)2]·2H2O and cis-[Cd(H 2O)2(phen)2] 3810. https://​doi.​org/​10.​1002/​cctc.​20200​0360
(H2Or)2·2H2O. Polyhedron 26:3669–3674. https://​doi.​org/​10.​ 59. Zhao H, Yuan ZY (2017) Transition metal–phosphorus-based
1016/j.​poly.​2007.​03.​060 materials for electrocatalytic energy conversion reactions. Catal
45. Yang G-Y, Sevov SC (2001) [Co(en)3][B2P3O11(OH)2]: a novel Sci Technol 7:330–347. https://​doi.​org/​10.​1039/​C6CY0​1719C
borophosphate templated by a transition-metal complex. Inorg 60. Agilent (2010) CrysAlis PRO. Agilent Technologies, Yarnton,
Chem 40:2214–2215. https://​doi.​org/​10.​1021/​ic001​397a England
 Journal of Applied Electrochemistry

61. Altomare A, Burla MC, Camalli M, Cascarano GL, Giacovazzo 77. Marchewka MK, Drozd M (2012) Ethylenediammonium dica-
C, Guagliardi A, Moliterni AGG, Polidori G, Spagna R (1999) a tion: H-bonded complexes with terephthalate, chloroacetate,
new tool for crystal structure determination and refinement. J Appl phosphite, selenite and sulfamate anions. Detailed vibrational
Cryst 32:115–119. https://​doi.​org/​10.​1107/​S0021​88989​80077​17 spectroscopic and theoretical studies of ethylenediammonium
62. Palatinus L, Chapuis G, (2007) A computer program for the solu- terephthalate. Spectrochim Acta A 99:223–233. https://​doi.​org/​
tion of crystal structures by charge flipping in arbitrary dimen- 10.​1016/j.​saa.​2012.​09.​026
sions. J Appl Cryst 40:786–790. https://​doi.​org/​10.​1107/​S0021​ 78. Akouibaa M, Lakkab I, Direm A, Lachkar M, Ouarsal R, Rakib
88980​70292​38 S, Nasif V, Sayin K, Morley N, El Bali B (2023) [­Cu 2(ox)
63. Petříček V, Palatinus L, Plášil J, Dušek M (2023) Jana 2020–a (dien)2](NO3)3, a precursor for preparation of CuO nanopar-
new version of the crystallographic computing system Jana. Z ticles: synthesis, structural, Hirshfeld surface analyses, and
fur Krist Cryst Mater. https://​doi.​org/​10.​1515/​zkri-​2023-​0005 physico-chemical investigations. J Mol Struct 1282:135258.
64. Brandenburg K, Putz KH (2005) DIAMOND. Version 3. Crystal https://​doi.​org/​10.​1016/j.​molst​r uc.​2023.​135258
impact GbR, Bonn, Germany 79. HighScore Plus | XRD Analysis Software | Malvern Panalyti-
65. Chen L, Sagar RUR, Chen J, Liu J, Aslam S, Nosheen F, Anwar cal. https://​www.​malve​r npan​alyti​cal.​com/​en/​produ​cts/​categ​ory/​
T, Hussain N, Hou X, Liang T (2021) Cobalt phthalocyanine softw​are/x-​ray-​diffr​action-​softw​are/​highs​core-​with-​plus-​option
as an efficient catalyst for hydrogen evolution reaction. Int J (accessed 17 Sept 2020)
Hydrog Energy 46:19338–19346. https://​doi.​org/​10.​1016/j.​ijhyd​ 80. Gates-Rector S, Blanton T (2019) The powder diffraction file: a
ene.​2021.​03.​075 quality materials characterization database. Powder Diffr 34:352–
66. Escobal J, Pizarro JL, Mesa JL, Arriortua MI, Rojo T (2000) 360. https://​doi.​org/​10.​1017/​S0885​71561​90008​12
An ionic nickel (II) phosphate with ethylenediamine:(C2H10N2) 81. Dolenko TA, Burikov SA, Dolenko SA, Efitorov AO, Plastinin IV,
[Ni(H2O)6](HPO4)2. Hydrothermal synthesis, crystal structure, Yuzhakov VI, Patsaeva SV (2015) Raman spectroscopy of water–
and spectroscopic properties. J Solid-State Chem 154:460–465. ethanol solutions: the estimation of hydrogen bonding energy and
https://​doi.​org/​10.​1006/​jssc.​2000.​8865 the appearance of clathrate-like structures in solutions. J Phys
67. Shan Y, Huang SD (1999) ­( C 2H 10N 2)[Co(H 2O) 6](HPO 4) 2: a Chem A 119:10806–10815. https://​doi.​org/​10.​1021/​acs.​jpca.​
supramolecular three-dimensional hydrogen-bonding network. 5b066​78
Acta Crystallogr C 55:921–923. https://​doi.​org/​10.​1107/​S0108​ 82. Ito H, Sone K (1985) On the assignment of band II in the elec-
27019​90015​84 tronic spectrum of [Ni(H2O)6]2+. Bull Chem Soc Jpn 58:2703–
68. Witty M, Dingra NN, Abboud KA, Felts AC, Na Ayudhya TI 2704. https://​doi.​org/​10.​1246/​bcsj.​58.​2703
(2017) Nuclear magnetic resonance and X-ray crystallography 83. Fernández S, Mesa JL, Pizarro JL, Lezama L, Arriortua ML,
to improve struvite determination. Anal Lett 50:2549–2559. Rojo T (2002) Two new three-dimensional vanadium (III) and
https://​doi.​org/​10.​1080/​00032​719.​2017.​13024​59 iron (III) phosphites templated by ethylenediamine:(C2H10N2)0.5­
69. Steiner T (2002) Die wasserstoffbrücke im festkörper. Angew [M(HPO3)2]. Ab initio structure determination, spectroscopic, and
Chem 114:50–80. https://​d oi.​o rg/​1 0.​1 002/​1 521-​3 757(20020​ magnetic properties. Chem Mater 14:2300–2307. https://​doi.​org/​
104)​114:1%​3c50::​AID-​ANGE50%​3e3.0.​CO;2-H 10.​1021/​cm011​2845
70. Shreif A, Farag MA, El-Sherbiny MA, Hassaan MY (2023) 84. Landry-Hum J, Bussière G, Daniel C, Reber C (2001) triplet
Effect of Zr ions on the structure and optical properties of electronic states in ­d2 and ­d8 complexes probed by absorption
lithium borosilicate molybdate glass system. Ceram Int spectroscopy: a CASSCF/CASPT2 analysis of [V(H2O)6]3+ and
49:8709–8717 [Ni(H2O)6]2+. Inorg Chem 40:2595–2601. https://d​ oi.o​ rg/1​ 0.1​ 021/​
71. Gharbi A, Jouini A, Averbuch-Pouchot MT, Durif AJ (1994) ic001​0860
Ethylenediammonium bis [copper(II) monohydrogendiphos- 85. Bussière G, Reber C (1998) coupled excited states in nickel (II)
phate ethylenediamine]trihydrate. J Solid-State Chem 111:330– complexes probed by polarized absorption spectroscopy. J Am
337. https://​doi.​org/​10.​1006/​jssc.​1994.​1235 Chem Soc 120:6306–6315. https://​doi.​org/​10.​1021/​ja974​0733
72. Dolphin D, Wick AE (1977) Tabulation of infrared spectral 86. Hassani HO, Al Wadaani FT (2018) Preparation, characterization
data. John Wiley and Sons, New York and catalytic activity of nickel molybdate ­(NiMoO4) nanoparti-
73. Nakamoto k, (1997) Infrared and Raman spectra of inorganic cles. Molecules 23:273. https://d​ oi.o​ rg/1​ 0.3​ 390/m
​ olecu​ les23​ 0202​
and coordination compounds. John Wiley & Sons, New York 73
74. Berg RW, Rasmussen K (1971) Vibrational spectra of ethyl-
enediamine salts. I. Tentative assignments of infrared and far Publisher's Note Springer Nature remains neutral with regard to
infrared spectra. Spectrosc Lett 4:285–293. https://​doi.​org/​10.​ jurisdictional claims in published maps and institutional affiliations.
1080/​00387​01710​80646​52
75. John M, Santha N, Nayar VU, Keresztury G (1993) Vibrational Springer Nature or its licensor (e.g. a society or other partner) holds
spectroscopic studies of Sr[(CH2)2(NH3)2]3P4O12⋅14H2O. Indian exclusive rights to this article under a publishing agreement with the
J Phys 67:413–420 author(s) or other rightsholder(s); author self-archiving of the accepted
76. Angeloni L, Marzocchi CE, MP, (1977) Single crystal vibra- manuscript version of this article is solely governed by the terms of
tional studies of hydrogen bonding in ethylenediammonium such publishing agreement and applicable law.
chloride. Chem Phys 26:257–265. https://​doi.​org/​10.​1016/​0301-​
0104(77)​87050-X