Removal of Multiple Contaminants from Water by Polyoxometalate

Supported Ionic Liquid Phases (POM‐SILPs)

Dr. Sven Herrmann 

Dr. Laura De Matteis 

Dr. Jesús M. de la Fuente 

Dr. Scott G. Mitchell 

Prof. Dr. Carsten Streb

First published: 12 January 2017

https://doi.org/10.1002/anie.201611072

Citations: 59

Abstract
The simultaneous removal of organic, inorganic, and microbial contaminants from water by one
material offers significant advantages when fast, facile, and robust water purification is required.
Herein, we present a supported ionic liquid phase (SILP) composite where each component targets
a specific type of water contaminant: a polyoxometalate‐ionic liquid (POM‐IL) is immobilized on
porous silica, giving the heterogeneous SILP. The water‐insoluble POM‐IL is composed of
antimicrobial alkylammonium cations and lacunary polyoxometalate anions with heavy‐metal binding
sites. The lipophilicity of the POM‐IL enables adsorption of organic contaminants. The silica support
can bind radionuclides. Using the POM‐SILP in filtration columns enables one‐step multi‐
contaminant water purification. The results show how multi‐functional POM‐SILPs can be designed
for advanced purification applications.

Water filtration devices produce safe drinking water from polluted surface or ground‐water
sources and are important when no central water‐purification facilities are available, for example,
in developing countries, in remote areas, or after environmental or industrial disasters.1 To‐date,
many rivers in developing countries carry high pollutant concentrations but are still used as a
source of drinking water.2, 3 Water treatment requires the removal of chemical pollutants, such as
toxic organics or inorganics (e.g. dyes, heavy metals, radionuclides) as well as microbial
contamination (e.g. E. coli).4 Typically, several filter components are connected in line, each
fulfilling a specific pollutant removal task, often using solid‐state adsorbents, such as clays,
zeolites, or activated carbon as the active materials.5 In contrast, tunable molecular components
are thus far not broadly employed for water purification as their use in technological settings is
often challenging owing to stability or compatibility issues.1, 6

Herein, we describe a materials design approach which enables the incorporation of molecular
components into multi‐functional composites, leading so‐called supported ionic liquid phases
(SILPs).7-9 In SILPs, a solid porous or non‐porous substrate, for example, silica is used to adsorb
an ionic liquid (IL), giving a solid composite whose properties can be tuned by chemical
modification of each component.10 This flexibility has led to SILP applications in heterogeneous
catalysis,11, 12 functional membranes13, 14 and product separation8, 13, 14 where the high SILP surface
area enables fast mass transfer. Further, SILPs allow the heterogenization of molecular species
within a supported IL, giving composites for advanced synthesis,15, 16 catalysis,10, 17 energy
storage,18 and green chemistry.19, 20

In this study, we have focused on polyoxometalate‐ionic liquids (POM‐ILs) which offer several
key properties required for water decontamination:21, 22 POM‐ILs are based on early, high‐valent
transition‐metal oxo anions (polyoxometalates) and bulky organic cations such as organic
ammonium, phosphonium, or imidazolium.21 Pioneering studies have used POM‐ILs as self‐
separating epoxidation catalysts,23 industrial catalysts for large‐scale petrochemical
processes,24 catalysts for solar energy conversion,25 or self‐repairing corrosion protection
coatings.26 Herein, lacunary polyoxotungstate anions capable of metal‐ion binding27 are combined
with antimicrobial tetraalkyl ammonium cations.28, 29 The resulting POM‐ILs are hydrophobic,
water‐immiscible and form stable films on surfaces,26 making them well suited for the removal of
organic, inorganic, and microbial pollutants from water. Further, the structural and compositional
tuning of the POM anions22, 30, 31 and organic cations10 is well established and can be used for
modifying the POM‐IL properties.

Thus far, POM‐IL‐based SILPs (POM‐SILPs) have not been reported, therefore we describe the
first POM‐SILP synthesis route: First, POM‐ILs are prepared using a modified route,26 in which
lacunary Keggin ions featuring pre‐designed heavy‐metal binding sites ([α‐SiW11O39]8−)27 are
combined with antimicrobial tetra‐n‐alkyl ammonium cations28, 29 (Q6=(n‐C6H13)4N+; Q7=(n‐
C7H15)4N+) to give highly viscous, lipophilic ionic liquids (Qx)8[α‐SiW11O39] (=(Qx)8{SiW11}; x=6,7;
Figure 1, see Supporting Information for synthetic details).26 POM‐SILPs were then prepared by
immobilization of the POM‐ILs on commercial porous silica (pore size 60 Å; particle size 60–
200 μm): to this end, the respective POM‐IL was dissolved in acetone, the silica particles were
dispersed in the solution, and the material was vacuum‐dried, giving the POM‐SILPs 1 a (based
on Q6) and 1 b (based on Q7), each featuring a POM‐IL loading of 21 wt % (see Supporting
Information for synthetic/analytical details). Non‐modified silica was used as a reference
throughout this study. All POM‐SILPs were obtained as dry, free‐flowing powders, allowing
facile handling and deployment. Analysis of the specific surface area (BET‐N2‐adsorption, see
Supporting Information) showed a decrease of the pore diameter and pore volume of the POM‐
SILPs with respect to the non‐modified silica reference, indicating POM‐IL adsorption on the
external surface and the internal pore walls of the silica.

Figure 1
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Water purification using polyoxometalate supported ionic liquid phases (POM‐SILPs) based on
lipophilic POM‐ILs supported on porous silica. The POM‐SILP column filter removes toxic
heavy metals (e.g. Ni2+, Pb2+, UO22+), aromatic organic pollutants (trityl dyes), and microbial
pathogens (E. coli) based on the presence of antimicrobial tetraalkyl ammonium cations and
lacunary polyoxometalate anions with specific metal binding sites (orange arrow).

The performance of POM‐SILPs for water purification was tested using filtration columns where
a glass Pasteur pipette was filled with 1 a, 1 b, or the non‐modified silica reference (ca. 800 mg,
see Figure 1). Rinsing of the filter columns with water showed that no leaching of the POM
anion or organic cation is detected using inductively coupled plasma atomic emission
spectroscopy (ICP‐AES) and CHN elemental analysis. The removal of the heavy metals Pb2+,
Ni2+, Cu2+, Cr3+, and Co2+ from water was tested by passing the respective pollutant solution
through the column (Figure 1). The chosen metals are major surface‐water contaminants
associated with involuntary industrial release into the environment.2 To simulate high
contamination, the cation concentrations were set to levels up to 45 000 times higher than the
World Health Organization (WHO) guideline levels (Table 1).32 The filtration tests were
 performed by passing aqueous solutions of the respective cation through the column (flow rate
ca. 6 mL min−1). Elemental analysis of the filtered solutions using ICP‐AES showed metal cation
removal between 78–100 % by the POM‐SILPs while significantly lower uptake was observed
for the non‐modified silica reference (Table 1, entries 1–6). Subsequent rinsing of the filters with
water (5 mL) showed no leaching of the heavy metals or the POM anions within the instrument
detection range (using ICP‐AES).

Table 1. Pollutant removal properties of the POM‐SILPs and the non‐modified silica reference.[a]

Entry POM‐SILP Pollutant [WHO  Pollutant removal by POM‐SILP [non‐

filter guideline level]32 modified silica] (mol %)[a]

1 1 a Pb2+ (2.2 mM) [0.05 μM] 99 [57]

3 1 a Ni2+ (1.3 mM) [0.34 μM] 89 [56]

4 1 a Cu2+ (1.3 mM) [30 mM] 100 [49]

5 1 a Cr3+ (1.2 mM) [0.96 μM] 78 [26]

6 1 a Co2+ (1.3 mM) [–] 80 [37]

7 1 b UO22+ (430 μM) [0.59 μM] 100 [100]

9 1 b PBV (32 μM)[b] [–] 95 [4]

 [a] V filtration =10 mL; flow rate≈6 mL min ; column: plugged glass Pasteur pipette (15 cm×7 
−1

mm, filled with ca. 800 mg 1 a, 1 b, or silica); [b] Patent Blue V.

Aqueous samples containing uranium(VI) (UO22+, Table 1, Entry 7) were used to examine the use
of POM‐SILPs in radionuclide removal from water,32 as previous reports have shown that silica
is capable of radionuclide adsorption.33 Under standard filtration conditions, the non‐modified
silica removes 100 % of the uranyl cations. Identical results were observed for the POM‐SILP 1 
b column, highlighting that the uranyl removal capability is retained after POM‐IL modification
of the silica.

To assess the effect of the metal binding site in POM‐SILP 1 b, we compared the Ni2+ uptake
capacity of 1 b with the (Q7)4[SiW12O40]‐based POM‐SILP 2 (POM‐loading: 21 wt %), where no
metal‐binding site is present on the Keggin anion. The study was targeted at separating the
effects of chemisorption (i.e. specific metal uptake into the vacant binding site of {SiW11} in 1 b)
and physisorption (i.e. dissolution of the metal cation in the POM‐IL) in 1 b and 2. To this end,
three batches of aqueous Ni2+ solutions (180 μM) were passed over columns filled with 1 
b or 2 respectively. Metal cation binding was determined by ICP‐AES. As shown in Figure 2, in
Filtration 1, both columns bind almost identical amounts of Ni2+ (removal ca. 83 %); in Filtration 
2 and Filtration 3, significantly higher Ni2+ removal is observed for 1 b compared with 2. We
propose that this significant difference in metal cation binding capacity is due to the specific
metal‐binding sites present in 1 b which are absent from 2, resulting in reduced overall metal
uptake by 2.

Figure 2
Open in figure viewerPowerPoint
Ni2+ removal by POM‐SILPs 1 b and 2 illustrating the higher removal capacity of the {SiW11}‐
based 1 b which features a specific metal binding site. Conditions: aqueous solution, [Ni2+]=180 
μM; Vfiltration=10 mL per run.
The removal of organic pollutants from water was examined using the dye patent blue V (PBV,
Figure 3) as a model for water soluble organic triphenyl methane (trityl) derivatives used in
textile manufacture.34 To this end, aqueous solutions of PBV were filtered over POM‐SILP 1 
b using the standard filtration setup described above. Dye removal was assessed by UV/Vis
spectroscopy (Figure 3) and it was shown that the POM‐SILP 1 b removes 95 % of the dye while
the non‐modified silica reference showed only 4 % removal (Table 1, Entry 9). Chemical
considerations suggest that the increased dye removal by 1 b is due to the high lipophilicity of
POM‐ILs26 whereas the hydrophilic silica does not interact strongly with the aromatic dye.
Rinsing of the POM‐SILP filter with water (5 mL) showed no leaching of the dye or POM into
the aqueous phase (using UV/Vis).

Figure 3
Open in figure viewerPowerPoint
a) Removal of the aromatic model pollutant Patent Blue V (PBV) from water by filtration using
POM‐SILP 1 b or pure silica as column materials. Inset: Photographs of the solution before and
after filtration over 1 b and molecular structure of PBV. b) Photograph of the filter column (1 b)
after filtration. Conditions: [PBV]=32 μM; Vfiltration=10 mL.

Finally, the removal of microbial contamination from water by the POM‐SILP filtration columns
was examined. Initial studies investigated the general antimicrobial effect of the POM‐IL
(Q7)8{SiW11} against Escherichia coli (E. coli) using a dispersion of (Q7)8{SiW11} or POM‐
SILP 1 b in Luria–Bertani (LB) growth medium at different POM‐IL or POM‐SILP
concentrations (Figure 4, Top). These in vitro cell proliferation assays measure the bacteria cell
density in suspension, thereby quantifying bacterial growth over the incubation period (8 h). The
dispersed pure POM‐IL (Q7)8{SiW11} showed high antimicrobial activity and full inhibition of
bacterial growth was observed at concentrations of 0.50 mg mL−1 and higher. Compound 1 b also
showed antimicrobial activity, however, full bacteria growth inhibition was only observed at
POM‐SILP concentrations of 4.8 mg mL−1. At 21 wt % POM‐IL loading, this equates to a
(Q7)8{SiW11} concentration of 1 mg mL−1, that is, double the concentration required for the non‐
silica‐supported POM‐IL.

Figure 4
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Top: E. coli growth curves (109 CFU mL−1 in LB medium) at different concentrations of POM‐IL
(Q7)8{SiW11} (a) and the POM‐SILP 1 b (b). Note that for comparison, in (b) the POM‐SILP
concentration is given together with the concentration of the active POM‐IL (21 wt %) and the
control references in both graphs refer to E. coli (109 CFU mL−1) in LB medium with 1 % DMSO.
Bottom: Microbial decontamination efficiency of filtration columns based on POM‐SILP 1 b or
non‐modified silica. Each column was loaded with aqueous E. coli solution (0.5 mL, 109 CFU 
mL−1) and the column was eluted with 2.5 mL of water. The recyclability was tested by
performing three consecutive E. coli removal runs per column (Filtration 1–3).

Based on these initial findings, filtration experiments were carried out using filtration columns
containing POM‐SILP 1 b. As reference, identical filtration experiments over non‐modified
silica columns were performed: briefly, an E. coli suspension (microbial content 109 CFU mL−1)
was filtered through the POM‐SILP column and the column was then rinsed with a total of 2.5 
mL of water to recover any residual bacteria (Figure 4, Bottom). The viable microbial content of
the filtrate was analyzed using standard resazurin colorimetric assays (see Supporting
Information).

As shown in Figure 4, Bottom, the POM‐SILP 1 b columns showed high efficiencies (>90 %) for
the decontamination of E. coli in water. In contrast, the pure silica columns showed no
significant removal of bacterial cells (decontamination efficiency <20 %), confirming that the
decontamination properties are associated with the presence of the POM‐SILP 1 b. The
recyclability of the filter column was tested by filtration of two further aqueous 109 CFU mL−1 E. 
coli suspensions as described above over the original columns (Filtration 2 and 3, see Figure 4,
Bottom). Filtration 1 and 2 showed similar decontamination efficiencies (>90 %), while a drop in
efficiency to about 80 % was noted for Filtration 3, indicating that further work is needed to
increase antimicrobial efficiency if multi‐use filter columns are desired.

In conclusion, we report a unique multi‐functional composite for the removal of organic,

inorganic, and microbial pollutants from water. A polyoxometalate–ionic liquid (POM‐IL)
featuring antimicrobial cations and metal‐binding anions is immobilized on silica, giving the first
example of a POM‐SILP (polyoxometalate supported ionic liquid phase). Toxic heavy metals
(e.g. Ni2+, Pb2+), nuclear waste (UO22+), organic aromatics (trityl dye), and microbes (E. coli) are
successfully removed from the water feed by the combined action of the POM‐SILP
components, opening new avenues for multi‐functional materials for pollutant adsorption and
water purification. Future work will focus on upscaling and prototype development, long time‐
scale testing, as well as detailed studies exploring the SILP performance when exposed to
multiple contaminants under real conditions.

Experimental Section
POM‐SILP preparation: the POM‐SILPs 1 a,b and 2 were prepared by dispersing silica particles
(4.8 g) in an acetone solution of the respective POM‐IL and removing the solvent under reduced
pressure. For detailed synthetic and analytical information, see Supporting Information.
Filtration experiments: A glass Pasteur pipette was filled with ca. 800 mg of the respective
adsorbent. Aqueous solutions (10 mL) containing the respective pollutant were passed over the
filter column (flow rate ca. 6 mL min−1) and adsorption of the respective pollutant was
determined by ICP‐AES (heavy metals) or UV/Vis spectroscopy (PBV). For detailed description
see Supporting Information.

Conflict of interest
German utility patent pending.

Acknowledgements
Financial support by the Fonds der Chemischen Industrie FCI (S.H., C.S.), Fundación General
CSIC (S.G.M., Programa ComFuturo), Fondo Social Europeo‐Gobierno de Aragón (J.M.F,
L.D.M. and S.G.M.), EU COST Action CM1203 (S.G.M., C.S.) and Ulm University (S.H., C.S.)
is gratefully acknowledged.