Two Ni/Co-substituted sandwich-type germanomolybdates based on an unprecedented trivacant polyanion [α-GeMo10O36]8-

Article abstract of DOI:10.1039/c9dt04433g

Two Ni/Co-substituted sandwich-type germanomolybdates, {[M₃(NH₂-trz)₆(H₂O)₆][M₄(H₂O)₂(HGeMo₁₀O₃₆)₂]}·nH₂O (M = Ni²⁺

Full text of DOI:10.1039/c9dt04433g

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Two Ni/Co-substituted sandwich-type germanomolybdates based
on unprecedented trivacant polyanion [α-GeMo10O36]8-
Hui Xu,a Xing-Man, Liu,c Tan Su,*a,b Wei-Chao Chen,c and Zhong-Min Su*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Two Ni/Co-substituted sandwich-type germanomolybdates, species to build novel sandwich-POMs.18-22 To date, lacunary
{[M3(NH2-trz)6(H2O)6][M4(H2O)2(HGeMo10O36)2]}·nH2O (M = Ni2+ (1) Keggin heteropolygermantungstates (HPTs) have been
and Co2+ (2), n = 10 (1) or 11 (2), NH2-trz = 4-amino-1,2,4-triazole), extensively reported.23-27 In contrast, a minority of research
have been obtained under hydrothermal conditions. 1 and 2 efforts have been devoted to heteropolymolybdates analogues
represent the first trivacant Keggin germanomolybdates involving (HPMs) mainly because of the instability of the HPMS in
unprecedented [α-GeMo10O36]8- fragments and {M3O4} quasi- aqueous than that of HPTs.28 In particular, only few lacunary
cubane building units. Both of them exhibit electrocatalytic Keggin germanomolybdates have been studied by Xu’s group,
behaviours of reduction H2O2 and photocatalytic properties for Niu’s group and Yang’s group.29-33 These reported lacunary
CO2 conversion.
germanomolybdates are mainly focused on the trivacant (1:9)
and the monovacant (1:11) species. While, investigations on
the trivacant (1:10) germanomolybdate fragments with TM
atoms incorporated vacant sites of the POMs have not been
explored. Consequently, further exploration new building
block for the design and construction complex structures will
be a meaningful work.
Lately, we began to explore the lacunary germanomolybdate
systems based on the following considerations: First, it is quite
difficult to previously synthesize lacunary germanomolybdate
precursors. Most of reported sandwich germanomolybdates
are synthetized by using Na2MoO4·2H2O/(NH4)6Mo7O24·6H2O,
GeO2, or H4[GeMo12O40]·14H2O as the starting materials by
complicated multi-step reaction using HAC-NaAC buffer
solution even organic solvent (i.e. CH3CN) by the method of
evaporation solvent (Table S8). In order to simplify the
reaction step and shorten the crystal growth time, we
employed the one-step reaction method and selected
(NH4)6Mo7O24·4H2O and GeO2 as starting materials by in situ
self-assembly reactions to prepare [α-GeMo10O36]8- polyanions.
Second, the hydrothermal synthesis is a common technique
for the synthesis of novel POM-based organic-inorganic
hybrids. Herein, by a one-step reaction method and the simple
starting materials, we successfully isolate two Ni/Co-
Polyoxometalates (POMs) represent a family of polyanionic
metal-oxo clusters consisted of high oxidation early transition
metals (e.g. Mo, W, V, Nb and Ta).1-3 POMs possess unmatched
physical and chemical properties and their transferable
building blocks are able to utilize for the construction of new
materials.4 Interestingly, they can undergo reversible multi-
electron redox conversion without their structural changes
under mild conditions and can be applied as photo- and
electro-catalysts.5,6 The introduction of transition metal atoms
and organic ligands to POMs is beneficial to fine-tuning of their
catalytic performances.7 Furthermore, some organic–inorganic
POM-based hybrid materials are promising catalysts because
they are more stable in polar solvents than other crystalline
materials.8 Sandwich-type POMs with cubane or quasi-cubane
metal units as catalysts have be widely applied in green energy
systems especially in the field of photocatalysis and
electrocatalysis.9-17 From this, the design of unique organic–
inorganic hybrid materials based on sandwich-type POMs
inspired our interest.
Lacunary Keggin polyoxoanions usually act as multidentate
inorganic building blocks to incorporate transition metal
substituted
sandwich-type
trivacant
Keggin
a. College of Chemistry, Jilin University, Changchun 130012, PR China. E-mail:
zmsu@nenu.edu.cn.
germanomolybdates with unprecedented trivacant [α-
GeMo10O36]8- fragments. As far as we known, no similar unit
exists even in lacunary Keggin germanotungstate analogues
(Scheme S1†).34-48 The electrocatalytic behaviours of reduction
H2O2 and photocatalytic CO2 conversion activities for 1 and 2
have been investigated.
b. Institute of Theoretical Chemistry, Jilin University, Changchun 130021, PR China.
E-mail: sutan_jlu@jlu.edu.cn.
c. Department of Chemistry, Northeast Normal University, Changchun 130024, PR
China.
†Electronic Supplementary Information (ESI) available: Experimental methods,
supporting figures and tables. CCDC 1961645 (1) and 1961646 (2). For ESI and
crystallographic
data
in
CIF
or
other
electronic
format
see
DOI: 10.1039/x0xx00000x
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Crystal phase purities of 1 and 2 are verified by the two {Ni3O4} quasi-cubane building blocks with four edge-
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agreement between the experimental X-ray diffraction (PXRD) shared {NiO6} octahedra. Two Ni atoms DinO{I:N10i4.O101369}/Cu9nDitTs0e4a43te3Gd
patterns and the simulated curves from single crystal in two middle positions bonded by two [α-GeMo10O36]8-
structures (Fig. S1 and S2†). The structure analysis shows both polyoxoanion and the external two Ni atoms coordinated with
compounds crystallize in the same P-1 space group (Table S1†). two [α-GeMo10O36]8- polyoxoanion and two water molecules
1 and 2 exhibit similar structures except for different metal (Fig. 1e and f) (Ni–O: 2.037(4) – 2.086(4) Å). The adjacent
atoms, therefore 1 is depicted as a representative in detail. sandwich-type polyoxoanions are connected together with
The structure of 1 consists of one sandwich-type polyoxoanion, H2O molecules to give 1 D chains via hydrogen bonds
one counter [Ni3(NH2-trz)6(H2O)2]6+ cation, and ten lattice (O(4W)…O(10W) 2.603(6) Å and O(4W)…O(30) 2.724(6) Å). The
water molecules (Fig. 1a). The counter [Ni3(NH2-trz)6(H2O)]6+ neighbouring 1 D chains are bonded by two H2O molecules via
cluster is made up of three Ni atoms and six NH2-trz ligands hydrogen bonds (O(7W)…O(13) 2.871(15) Å and O(7W)…O(5)
(Fig. 1b). The terminal Ni4 and Ni4A atoms are coordinated by 2.835(15) Å) to generate a 2D supramolecular layer with 1D
three water molecules and three NH2-trz ligands, respectively. channels. Interestingly, the counter [Ni3(NH2-trz)6(H2O)]6+
The Ni3 atom as the point of junction joined to six NH2-trz cluster are filled in these channels via hydrogen bonds
ligands (Ni–N: 2.037(4)–2.103(4) Å). The sandwich-type (O(7W)…O(3W) 2.672(9) Å). The close-packed 3D
polyoxoanion is built by two trivacant [α-GeMo10O36]8-
fragments and a rhomb-like {Ni4O16} unit. The trivacant [α-
GeMo10O36]8- fragments originated from the lacunary [α-
GeMo9O34]10- heteropolyanions, by grafting one distorted
{MoO6} octahedron into an edge-sharing tri-metal cluster at
the polar position in a common angle connection mode
(Scheme S2†). The grafted Mo atom exhibits a six-coordinate
mode linking four μ2-O atoms and two Ot (terminal oxygen)
atoms (Fig. 1c and d) (Mo–O: 1.678 (4) – 2.396(3) Å). To our
knowledge, the trivacant Keggin [α-GeMo10O36]8- polyanion
cluster is first observed. The rhomb-like {Ni4O16} unit contains
Fig. 2 (a) 1 D chain of 1 based on sandwich-type polyoxoanions H2O
Fig. 1 (a) The structure unit in 1; (b) The coordination modes
of Ni atoms in the [Ni3(NH2-trz)6(H2O)]6+ cation cluster; Ball-
and-stick model (c) and (d) polyhedron of trivacant-Keggin [α-
GeMo10O36]8- polyanion cluster; (e) The coordination modes
of {Ni4O16} unit in sandwich-type polyoxoanions; (f) {M3O4}
quasi-cubane building units with four edge-sharing NiII
octahedral. Ni, green; Mo, light blue; Ge, yellow; O, red; C,
gray; N, blue.
molecules connected via hydrogen bonds; (b) View of 2D layer
structure connected through the hydrogen bond in 1; (c) View of a
close-packed 3D supramolecular network in 1.
supramolecular network was constructed by hydrogen bonds
(O(1W)…O(1) 2.673(6) Å and O(9W)…O(6) 2.818(4) Å) between
adjacent layers (Fig. 2).
2 | J. Name., 2012, 00, 1-3
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The IR spectra of 1 and 2 show similar characteristic peaks The thermal stabilities of two compounds were eVxipewloArreticdle fOrnolimne
DOI: 10.1039/C9DT04433G
derived from Keggin-type frameworks (Fig. S3 and S4†). Four 25 to 800 °C under nitrogen atmosphere. The TGA curves of 1
characteristic peaks are corresponded to ν(Mo–Od), ν(Ge–Oa), and 2 shows three weight losses progress. (Fig. S7 and S8†).
ν(Mo–Ob), and ν(Mo–Oc) at 938, 878, 785 and 712 cm-1 for 1; The first weight loss of 7.51% for 1 at 25–180 °C, and 8.40% for
939, 897/857, 782, 688 cm-1 for 2, respectively. The peaks at 2 at 25-190 °C corresponded to the loss of water molecules
615 cm-1 for
1 2 result from the (calculated value 7.27% for 10 H2O in 1 and 7.64% for 11 H2O
and 620 cm-1 for
antisymmetric stretching modes of Mo–Ob and Mo–Oc. The in 2). The second weight loss of 11.83% and 12.02% for 1 and 2
(calculated value 11.32% for 1 and 11.23% for 2) at 180–450 °C
corresponded to the loss of NH2-trz ligands. Above 690 °C, the
frames of 1 and 2 started to decompose. The experimental
values are in accord with calculation values of 1 and 2.
The UV-vis spectra of the two compounds were measured
from 200-800 nm (Fig. S9 and S10†). The two absorption peaks
at 246 and 288 nm for 1, 238 and 281 nm for 2 are observed.
The high energy bands are attributed to Od→Mo bands charge
transfer transitions, while the lower bands are ascribed to Ob(c)
→ Mo bonds charge transfer transitions.53,54 In the visible
range, 1 and 2 exhibit broad absorption bands at 550-650 nm,
which can be attributed to coordinated Ni2+ or Co2+.55,56 The
band gap energy (Eg) of 1 and 2 were obtained by measuring
diffuse reflection spectra of powder samples. The optical
absorption can be assessed at 2.71 eV for 1 and 2.94 eV for 2,
Fig. 3 Time-production plot of CO and H2 produced using (a) 1 or
(b) 2 under visible irradiation.
vibration peaks at 3315 and 3115 cm-1 for 1; 3308 and 3111
cm-1 for 2 can be attributed to the stretching modes of -NH2
and -CH2 of NH2-trz, respectively. And the peaks at 1540 and
1430cm-1 for 1; 1542 and 1395 cm-1 for 2 can be assigned to
the bending vibration characteristic peaks of NH2 and CH2,
respectively.32
Bond valence sum (BVS) calculations (Table S6 and S7†)
prove the oxidation states of all Mo atoms of 1 and 2 are +6.
The oxidation states of Co atoms in 1 and Ni atoms in 2 are +2.
The calculations results are in accord with the X-ray
photoelectron spectroscopy (XPS) (Fig. S5 and S6†). Two peaks
at 232.5 and 232.2 eV for 1, and 235.6 and 235.4 eV for 2 are
assignable to Mo6+ (3d5/2) and Mo6+ (3d3/2).49,50 For 1, two
peaks at 856.0 and 873.5 eV can be attributed to Ni2+(2p3/2
)
Fig. 4 The influence of the water content on the photocatalytic
CO2 reduction in
unchanged).
and Ni2+ (2p1/2), respectively.51 As for 2, two peaks at 781.3 and
1
or
2
(the total solvent volume was
797.4 eV corresponded to Co2+ (2p3/2) and Co2+ (2p1/2).52
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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indicating the two compounds possess semiconductor In summary, we reported two Ni/Co-substituted sandwich-
View Article Online
DOI: 10.1039/C9DT04433G
properties (Fig. S11 and S12†).
type germanomolybdates based on unprecedented trivacant
The CO2 photoreduction experiments of 1 and 2 were trivacant [α-GeMo10O36]8- fragments and {M3O4} quasi-cubane
conducted with pure CO2 atmosphere in MeCN/H2O mixed building units using the one-step reaction method under
solution
including
triethanolamine
(TEOA)
and hydrothermal conditions. 1 and 2 have efficient photocatalytic
[Ru(bpy)3]Cl2·6H2O (bpy = 2’2-bipyridine) under visible-light CO2 redcution properties and the electrocatalytic activities to
irradiation. Within 3 h illumination, CO and H2 were the main reduce H2O2. This work provides an effective and feasible
gas products were detected in gaseous phase. As shown in Fig. method to design and synthetize more trivacant
3, the evolution amount of CO and H2 continued to rise with germanomolybdates with desirable functionalities.
the increasing irradiation time. After 3 hours' irradiation, the
total amounts of CO and H2 reach 10.2 and 2.3 μmol for 1. In
contrast, the total evolved CO and H2 reach 17.6 and 10.8
Conflicts of interest
μmol for 2. Finally, the CO selectivity is 82% for 1, while 62%
for 2. This selectivity of 1 is much higher than that of most
heterogeneous catalysts with [RuII(bpy)3]2+ participation for
converting CO2 to CO listed in Table S9†. Moreover, no obvious
changes in the PXRD patterns and IR spectra were found after
the photocatalytic reaction, indicating the structural
robustness (Fig. S1-S4†). Control experiments were performed
to determine the significance of various reaction components
in CO2 reduction system (Table S10†). In the absence of
[Ru(bpy)3]Cl2, TEOA or light illumination, no gas products were
detected. In short of 1 or 2, only a trace amount of H2 was
generated, revealing the importance of 1 or 2 to this
photocatalysis system. When CO2 was replaced by ultrapure Ar,
only little H2 was generated, which reflects that the produced
CO stemmed from CO2 rather than organic decomposition.
When using DMF substitutes for MeCN in 1 or 2, the yields and
selectivity of CO remarkably lower than that the initial reaction
system. Moreover, we also investigate the influence of
sacrifice agent on the reaction by replacing the TEOA with TEA.
Furthermore, the catalytic activity depending on water
contents (5-30%) was also explored (Fig. 4). The amount of CO
generation increased to a maximum when the water content is
20%, but a sharp fall at higher contents of water. While, the
production of H2 increased with the raise of water contents.
The increase yield of H2 may be due to more H+ produced by
the large number of water molecules. The fall of CO yield is
probably the reason that the solubility of CO2 in water (ca.
0.034 M) is much lower than that in acetonitrile (0.279 M).57,58
The cyclic voltammetric behaviours of the two compounds
were investigated in 0.5 M H2SO4/Na2SO4 electrolyte solution
(Fig. S13 and S14†). The half-wave potentials E1/2 = (Epa + Epc)/2
are 0.258 (I–I′), 0.105 (II–II′) and -0.016 (III–III′) V for 1; 0.267
(I–I′), 0.095 (II–II′) and -0.043 (III–III′) V for 2, which can
attribute to the two electrons redox processes of the
MoVI/MoV.59 The peak currents were proportional to sweep
speed (from 50 to 400 mV s-1), revealing surface-confined
redox processes are dominative for the two compounds.60 The
electrocatalytic behaviours of 1 and 2 were also investigated.
As the amount of hydrogen peroxide increases, reduction peak
currents of 1 and 2 raised whereas the corresponding
oxidation peak currents decrease, indicating H2O2 was reduced
by 1 or 2 (Fig. S15†).
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the Financial Grant
from the China Postdoctoral Science Foundation (Grant ：
2017T100203 and 2018M631863), The Outstanding Youth
Talent Fund Project from Department of Science and
Technology of Jilin Province (Grant ： 20190103125JH), The
Fundamental Research Funds for the Central Universities
(2412019QD009 and 21601055).
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DOI: 10.1039/C9DT04433G
Graphical Abstract
Two Ni/Co-substituted sandwich-type germanomolybdates
based on unprecedented trivacant polyanion
[α-GeMo10O36]8-
Hui Xu,a Xing-Man, Liu,c Tan Su,*a,b Wei-Chao Chen,c and Zhong-Min Su*a
aCollege of Chemistry, Jilin University, Changchun, 130012, PR China
bInstitute of Theoretical Chemistry, Jilin University, Changchun 130021, PR China
cCollege of Chemistry, Northeast Normal University, Changchun 130024, PR China
Two
sandwich-type
germanomolybdates
with
unprecedented
trivacant
[α-GeMo10O36]8- fragments and {M3O4} quasi-cubane building units were obtained
for the first time. They exhibited electrocatalytic behaviours of reduction H2O2 and
photocatalytic properties for CO2 conversion.