Crystalline Framework Material Containing Arrays of Vanadium Oxide

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Crystalline Framework Material Containing Arrays of Vanadium Oxide Nanoclusters: A Polyoxovanadate Framework with Room Temperature NOx Sensing Properties M. Ishaque Khan, Naga Ravikanth Putrevu, Samar Ayesh, Elizabeth Yohannes, Brant Cage, and Robert J. Doedens Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg4007444 • Publication Date (Web): 18 Sep 2013 Downloaded from http://pubs.acs.org on September 20, 2013

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Crystal Growth & Design

Crystalline Framework Material Containing Arrays of Vanadium Oxide Nanoclusters: A Polyoxovanadate Framework with Room Temperature NO x Sensing Properties M. Ishaque Khan*,†, Naga Ravikanth Putrevu†, Samar Ayesh†, Elizabeth H. Yohannes†, Brant Cage†, Robert J. Doedens§ †

Department of Biological and Chemical Sciences, Illinois Institute of Technology Chicago, IL 60616, USA §

Department of Chemistry, University of California, Irvine, CA 92697, USA.

ABSTRACT: Transition metal oxide clusters provide attractive building blocks for synthesizing new materials with interesting structural, electronic and magnetic properties. An interesting framework structure material [CdII3 (H 2 O) 12 VIV 16 VV 2 O 36 (OH) 6 (AO 4 )]·24H 2 O (A= V, S), 1, composed of threedimensional arrays of vanadium oxide nanoclusters {V 18 O 42 (AO 4 )} interconnected by {-O-Cd-O-} bridging groups, has been prepared and characterized. Compound 1, whose structure is resolved at atomic level by single crystal x-ray structure analysis, exhibits properties suitable for gas sensing applications. Sensor devices fabricated from 1 show promising sensing properties for detecting environmentally detrimental {NO x } (NO and NO 2 ) gases with good sensitivity and reversibility. This is a rare example of a polyoxometalate based material showing room temperature NO x sensing properties.

KEYWORDS: Crystal structure, Polyoxometalates, Nitrogen oxides, Gas sensor

■ INTRODUCTION

Design and synthesis of crystalline materials with well-defined structures and controllable properties is both of fundamental and practical interest. This difficult problem has attracted considerable attention in recent years, fueled by the need to solve a wide range of environmental and technological challenges. A prominent example is of gas sensors where metal oxides are widely used for sensing a variety of gases such as NO, CO, CO 2 , O 2 , and H 2 S.1-8 While the size and shapes of commercial metal oxide gas sensors are fairly well optimized, their performance still limits their applications. It has not been possible to uniformly control the microstructure and surface properties of sensor materials and make subtle

modifications to these properties to optimize/control the sensor performance, especially the sensitivity and selectivity. In order to improve sensor performance, it will be necessary to control the structure of the sensor materials at the molecular level. It will also be useful to understand what surface, structural, electronic and magnetic properties influence interaction between analytes and sensor materials and how sensors work at the atomic and molecular level. To solve these problems, new generations of materials with superior properties are needed. And a better understanding of the fundamental structureproperty relationships at the molecular level is required for the rational synthesis of such functional materials. 1

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Transition metal oxide clusters or polyoxometalates (POM)9-15 provide access to a new class of materials that are promising to realize this goal. POMs are molecular systems with wideranging applications in the areas of green chemistry, detoxification of industrial chemicals, photocatalytic water splitting, catalysis, corrosion protection, electrooptics, analytical chemistry, biochemical and geochemical processes, and medicine.14-23 These giant clusters represent structure and bonding patterns observed in the infinite metal oxides24-27 which are widely used in chemical sensing and in catalyzing a large number of industrial chemical transformations of economic and environmental consequences.1-3,28-36 The suitability of many of the industrial metal oxide materials is determined empirically with little or no possibility of molecular level modifications in their structures to improve their performance. POMs provide attractive building blocks for constructing metal oxide based materials whose structures can be varied systematically and their properties, which can be studied by a variety of techniques, could be rationalized in terms of their constituents at the molecular level. A large number of these POMs of dimensions up to several nanometers and molecular weights at par with proteins are known,21-23 offering a rich variety of robust structural motifs of different sizes and topologies with well-defined structure and properties 21,24 for making such materials. We have been interested in the design and synthesis of functional materials composed of polyoxometalates37-39 building blocks whose structures can be readily modified at the molecular level. Here we describe the synthesis, crystal structure, magnetic properties, and NO x gas sensing properties of a new framework material [CdII3 (H 2 O) 12 VIV 16 VV 2 O 36 (OH) 6 (AO 4 )]·24H 2 O (A= V, S), 1, composed of polyoxovanadate nanoclusters {V 18 O 42 (AO 4 )} joined by {-O-Cd-O-} linker groups. Due to its interesting structural and electronic properties, the new material is likely to exhibit unique surface gas adsorption/reaction and, therefore, gas sensing properties. We constructed gas sensor devices from this material and selected environmentally

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detrimental nitrogen oxide NO x (NO+NO 2 ) gases as models to characterize the sensing behavior of the sensor devices. Preliminary data show that sensor devices fabricated from 1 respond to NO x gases at room temperature with good sensitivity, reversibility, and response and recovery time. To our knowledge, this is the first report on the low temperature NO x gas sensing properties of a polyoxometalate based framework material with atomically resolved well-defined structure which is suitable for structure-property relationship studies.

■ EXPERIMENTAL Synthesis of II IV V [Cd 3 (H 2 O) 12 V 16 V 2 O 36 (OH) 6 (AO 4 )]·24H 2 O (A= V, S), 1. Hydrazinium sulfate (2.5 mmol) was added to a hot (84-86 0C) aqueous solution (13 mL) of LiVO 3 (5 mmol), prepared by the reaction of the stoichiometric amount of V 2 O 5 (2.5 mmol) with LiOH·H 2 O (5 mmol) in water. The resulting mixture was heated under continuous stirring for 10 minutes to give a dark solution which was diluted to 25 mL with deionized water. The pH of the solution at this stage was 4.6. After adding 3CdSO 4 ·8H 2 O (1.25 mmol) to the diluted solution, it was further heated at 84-86 0C for 7 h. The resultant very dark solution, contained in a closed Erlenmeyer flask, was stored at room temperature for 12 h to give black prism-shaped crystals of 1 which were filtered from the near colorless mother liquor, washed with cold water, and dried at room temperature (yield 69% based on vanadium). Anal. Calcd for H 78 O 82 S 0.50 V 18.50 Cd 3 (1): S 0.59. Found: S 0.86. Prominent FT-IR peaks for 1 (KBr Pellet), cm-1: ν(H 2 O) = 3467 (s,b); ν (H 2 O) = 1618(s); ν(SO 4 ) = 1150(w), 1129(m); ν(V-O term ) = 987(s); ν as (VO 4 ) = 839(w), 797(m); ν as (V-(µ 3 O)) = 703(m), 628(m). Crystal Structure. Single crystal X-ray data were collected on a Bruker SMART-CCD 1K system. Crystals of 1 are cubic, space group Im3m (#229), with a = 15.675(2) Å. The structure refinement converged to R1 = 0.0303, wR2 = 0.0876, S = 1.28. Full experimental details and 2


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results of the structure determination are included in the deposited .cif file. Sensing Device Fabrication. A prototypical thick-film sensor device used in this work was prepared by the following general procedure: 200 mg of 1 was mixed with 10 drops (0.5ml) of deionized water. The resulting paste was used to deposit a 35-50 μm thick sensing film of 1 on a mica substrate (12 mm x 12 mm x 1.6 mm dimension) between two copper electrodes attached on top of the mica substrate. Gas Sensing Measurements in Air. For gas sensing experiments, the sensor device was placed inside a tubular quartz sensor cell placed in a tube furnace. NO (500 ppm in N 2 ) and NO 2 (100 ppm in N 2 ) (procured from Mittler Supply, Inc.) gases were used as probe gases for the evaluation of NO x sensing properties of the sensor device. The flows of air, N 2 , NO (500 ppm source tank), NO 2 (100 ppm source tank) through the sensor cell were controlled by OMEGA® precision variable area rotameters and digital mass flow controllers to form gas mixtures of various compositions, with a flow rate of 100 ml/min. Prior to the start of the sensor response measurements, sensor device was exposed to air for 4 hours for attaining sample equilibrium. The sensor response (measured as electrical resistance) to changes in the probe NO x gas concentrations was monitored by an Agilent Data Acquisition/Switch Unit (HP 34970A) and recorded by Agilent BenchLink Data Logger software on a Windows based PC. For dosage studies, NO gas was diluted with air to make the varying concentrations: 5, 10, 20, 50, 100, and 150ppm. In each experiment, the sensor was exposed to the NO gas of appropriate concentration for 5 min and then the gas stream was turned-off and sensor response, recovery time and sensitivity were determined. When the NO gas stream was turned off, air was allowed onto the device to displace the adsorbed probe gas molecules. Resistance readings were recorded and data were plotted against varying concentrations of the probe gas. A similar study was carried out for 100 ppm NO 2 gas. Gas Sensing Measurements under Helium Gas Atmosphere. In order to see any effect of air/oxgen on sensor response to NO x gases (in

the experiments involving NO x gas sensing measurements using the Agilent Data acquisition unit under air environment described in the above section), we carried out the NO x sensing measurements under He gas environments done in a Quantum Design Physical Properties Measurements system with a cryostat capable of maintaining temperatures from 1.8 K to 400 K. A helium environment was maintained by the following procedures: tubing connected the NO gas cylinder to a gas input port into the resistance probe consisting of a 5 mm ID waveguide that was sealed into a stainless steel cryostat chamber capable of mTorr vacuum. The chamber is part of a Quantum Design Physical Properties Measurements System connected to a vacuum pump and a helium input. The closed system was then purged to mTorr and filled with helium 9 times. The helium pressure was kept at about 2 Torr above atmosphere. The sample was allowed to equilibrate to the helium atmosphere before measurements were done. Sensor response upon exposure to NO x gases were measured as change in the electrical resistance using an ohmmeter under helium gas environment. For NO sensing experiments, pure NO gas was used as probe gas. And 100ppm NO 2 (diluted in N 2 gas) was used for NO 2 sensing measurements. The experimental temperatures were constant at 300 K and the environment composed entirely of high purity helium at pressures approximately 2 psi above ambient. The samples were allowed to equilibrate for an hour before exposure to the NO x gas. The NO x gas was introduced using a helium filled plastic tube connected with a gas waveguide adapter to a 3 x 5 mm inside dimensions brass coated silver electron paramagnetic resonance waveguide that entered the sealed cryostat and ended in a dispersion horn of approximately the same size as the sensor device. The sensor device was insulated from and attached about 5-10 mm away from the horn. The wiring was homemade and of the two wire type and the resistance was read by a Radio Shack 46 range PC interface digital multimeter and the results recorded on Dell PC.

■ RESULTS AND DISCUSSION

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Compound 1 is readily synthesized by procedures described in the experimental section. X-ray quality crystals of 1, which are essentially obtained from single-pot synthesis, are insoluble in common solvents and soluble in hot water. The dark color of the crystals, characteristic of the reduced and mixed-valence compounds, is indicative of the presence of vanadium (IV) sites. This was confirmed by the manganometric titration of the reduced VIV sites in 1 which revealed the presence of an average of 16VIV sites per {V 18 O 42 (AO 4 )} cluster in 1. The number of reduced vanadium (IV) sites in 1 decreases slowly upon exposure of the crystals in air. The elemental analysis of 1 is consistent with its formulation. The compound could not be prepared in the absence of sulfate ion in the reaction mixture. The infrared spectrum of 1 exhibits absorption bands in the regions characteristic of H 2 O, ν(SO 4 ), ν(VO 4 ), ν(V-O term ), and ν(V-(µ 3 O)) functionalities. The crystals of 1 are isomorphous with our previously reported manganese, iron, cobalt, and nickel analogs.37c,38,39 The crystal structure (Figures 1-2) consists of {V 18 O 42 } cages40 with crystallographic m-3m (O h ) symmetry linked into two interpenetrating 3-dimensional networks by bridging {-O-M{(H 2 O) 4 }-O} groups (M = Cd for 1). The origin of the interpenetrating structure lies in the bodycentering41. Inside each cage is a twofolddisordered tetrahedral {AO 4 } group. Bond distances involving the cage atoms, together with two important nonbonded contacts, are listed in Table 1. The twofold disorder of the AO 4 group gives it the same O h symmetry as the V 18 O 42 cage. The V1…O4 contact of 2.559(6) Ǻ is too long to be a covalent bond, but is likely to represent a weak attractive interaction. Each of the disordered O4 halfatoms participates in three such contacts to symmetry-equivalent V1 species. This pattern of contacts is consistent with the observed disorder. In the hypothetical case of an ordered central group, the symmetry of the {V 18 O 42 (AO 4 )}cage will not be higher than T d , requiring a lower symmetry space group (e.g., I43m). The short O central - O shell contact in such

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cases will lower the symmetry of the {V 18 O 42 } shell as previously observed.37b,40 The structures of the systems described here, however, neither refine well in the lower symmetry space groups nor do such refinements alleviate the disorder problem. Both vanadate and sulfate ions are present during the syntheses of these compounds and there is precedent for both as encapsulated anions in this cage species 37(c).

Figure 1. The cluster {V 18 O 42 (AO 4 )} in the crystals of II IV V [Cd 3 (H 2 O) 12 V 16 V 2 O 36 (OH) 6 (AO 4 )]·24H 2 O (A= V, S), (1) showing the atom labeling scheme. Thermal ellipsoids are drawn at 50% probability. Since solids composed purely of {V 18 O 42 (VO 4 )} and {V 18 O 42 (SO 4 )} clusters linked by bridging groups have also been prepared by us, 37a,37b,39 one may speculate the structure of 1 could consist of regular alternating {V 18 O 42 (VO 4 )} and {V 18 O 42 (SO 4 )} clusters. A structure of this type would, however, require the space group to be primitive rather than body-centered. Our attempts to refine these structures with alternating clusters in the corresponding primitive space group yielded unsatisfactory results, supporting the body-centered model. Also, the closely related nickel derivative, in which the cage contains only sulfate ions, crystallizes in the bodycentered space group.39 The water molecules bound to the bridging metal atom also exhibit a twofold disorder. Waters of solvation occupy the gaps between the {V 18 O 42 } cages. The 4


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hydrogen atoms of the one crystallographically independent water molecule were located on a difference Fourier map and demonstrate a twofold rotational disorder of the solvent about the O5-H5A bond. Symmetry elements generate a cyclic hexamer of water molecules. The water molecules are also hydrogen bonded via H5A to the cage oxygen atom O1. This arrangement is also found in the analogous nickel compound; views of the hexamer and its environment may be found in the report of the structure of that system.39

Figure 2. A view of the unit cell contents in the crystals of 1. The water molecules, the Li+ ions, and the encapsulated SO 4 /VO 4 groups are left out for clarity. A view, including displacement ellipsoids, of the [V 18 O 42 (AO 4 )] cage of 1 is shown in Figure 1. Bond distances (Table 1) within the cage are all normal. Another feature that is found in all of these linked cage compounds is an elongated displacement ellipsoid for the cage atom O1. The elongation is in the direction of a short O4…O1 contact of 2.454(9) Ǻ. Hence, it is reasonable that differences in the steric interaction of O1 with empty and occupied O4 sites could produce two incompletely resolved sites for O1. Table 1. Selected Interatomic Distances (Ǻ) in [CdII 3 (H 2 O) 12 VIV 16 VV 2 O 36 (OH) 6 (AO 4 )]·24H 2 O (A= V, S), (1)

Cd(1)-O(3) V(1)-O(1) V(1)-O(2) V(10…O(4) V(2)-O(1) V(2)-O(3) V(3)/S(1)-O(4) O(1)…O(4) V(2)-O(1)

2.229(6) 1.9596(14) 1.590(4) 2.559(6) 1.939(3) 1.620(6) 1.548(11) 2.454(9) 2.229(6)

Crystallographic and chemical data indicate that the AO 4 group is a disordered combination of SO 4 2- and VO 4 3- components. The A-O distance of 1.548(11) Å for 1 is intermediate between the expected values for sulfate and vanadate. The displacement parameter of A was unreasonably high when A was refined as 100% V and unrealistically low when only S was included. In preliminary refinements, displacement and occupancy parameters for A were refined alternately: in the final refinement, the displacement parameter of A was fixed at 0.012 Å2 and the relative proportions of V and S were allowed to vary. This model converged to approximately equal proportions of V and S (fraction of V = 0.45(4)). While different assumptions could change this value somewhat, an equal mixture of sulfate and vanadate is consistent with all data. The water of solvation in 1 is easily removable. The differential thermogram curve for 1 showed a strong sharp peak at 85.8 0C with 19.2% weight loss corresponding to the removal of lattice water (15.87% theoretical weight) and another medium intensity peak centered at 275.4 0 C showing 6.3% weight loss represents the loss of coordinated water (7.9% theoretical weight). In view of its structural and electronic properties, the mixed-valence species 1 is an attractive candidate with relevance to semiconducting sensors. We employed a thick film of 1 to prepare semiconducting sensing devices and evaluated its sensing properties for environmentally detrimental NO x gases.42 NO x Sensing Properties. NO and NO 2 gases were used as probe gases for evaluating NO x sensing properties of the device fabricated from 1. The sensor responded to the exposure of probe gases at room temperature in air. In the NO sensing study, as the NO gas concentration 5



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varied from 1 ppm to 150 ppm (1, 5, 10, 20, 50, 100, and 150ppm), the sensor resistance increased gradually with concomitant increase in the sensor response and recovery time. The lowest detection concentration was observed at 5ppm NO as shown in Figure 3.

Figure 4. Room temperature NO 2 gas sensing properties of 1 in air; Sensitivity at 20ppm is 0.03, response time at 20ppm is ~1.7min and recovery time at 20ppm is ~3.5min;Sensitivity at 100ppm is 0.33, response time at 100ppm is ~5min and recovery time at 100ppm is ~4.5min. Figure 3. Room temperature NO gas sensing properties of 1 in air; Sensitivity at 5ppm is 0.01, response time at 5ppm is ~3.5min and recovery time at 5ppm is ~13min; Sensitivity at 150ppm is 0.15, response time at 150ppm is ~2min and recovery time at 150ppm is ~21min. A similar trend in sensor response was observed when NO 2 was used as a probe gas in the concentration range of 1-100 ppm (NO 2 in N 2 ). However, the increase in concentration of NO 2 gas led to a relatively smaller increase in sensor resistance, indicating that the sensor material, 1, is relatively less sensitive towards NO 2 gas as compared to NO gas, as is shown in Figure 4. Furthermore, the detection limit (the minimum concentration) for NO 2 was higher than the NO gas. Sensor characteristics of compound 1 for NO and NO 2 gases are shown in Figures 3 and 4. Compound 1 showed higher sensitivity towards NO 2 gas whereas a lower detection limit (5ppm) was shown with NO gas. At the NO detection limit, 5ppm, the response and recovery times are ~3.5min and ~13min respectively.

In the NO 2 sensing studies at the detection limit, 20 ppm, the response and recovery times are ~1.7 min and ~3.5 min respectively. For both gases, the sensor recovery time increased with increase in the probe gas concentrations.

NO exposure

Figure 5. Sensor response of 1 to NO gas in helium environment.

In order to see if sensors response to NO x gases in an inert gas environment (where there is no interference from CO, CO 2 gases and humidity), we carried out NO x sensing experiments in helium gas environment. The result is shown in Figure 5. Clearly, the resistance of the sensor film of 1 increases upon exposure to NO gas. A similar trend was observed with NO 2 gas also, as shown in Figure 6. The increase in the resistance of the sensor film of 1 upon exposure to NO and NO 2 gases 6


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under the inert (helium) gas environment is qualitatively similar to the observed increase in sensor film resistance upon exposure to NO x gases in air.

NO2 exposure

Figure 6. Sensor response of 1 to NO 2 gas in helium environment. It is notable that exposure of sensor film 1 to both NO and NO 2 gases leads to an increase in the resistance in the air as well as in an inert atmosphere. This interesting behavior of a metal oxide based sensor is, however, not unprecedented. An earlier publication on tungsten oxide NO x sensing studies reported that WO 3 sensor resistance increased upon exposure to NO x gases.43 The room temperature NO x sensing attributes of 1 is of considerable interest from both fundamental and practical viewpoint. Current NO x sensors, which are based on metal oxides, exhibit sensing properties at much higher temperatures.44,45 For example WO 3 , which is the most commonly employed NO x sensing material, responds to NO x gases at a temperature of 200 oC.46-67 To our knowledge, 1 is the first example of a POM based welldefined structure material with promising NO x sensing properties. Compound 1 represents an interesting class of crystalline framework materials that respond to NO x gases at a relatively low temperature. The molecular building block approach which we employed to prepare it allows a systematic variation in the constituent POM cluster and/or the heterometallic atom M in the {-O-M-O-} linker group which can influence properties of the properties. This atomic and molecular level

control on the structure opens new opportunities for tuning the properties of the materials and studying structure-property relationships. A molecular level understanding of the structureproperty relationship can help develop new materials needed for improving sensor performance with enhanced sensitivity and selectivity. It has potential to produce materials suitable for low temperature NO x gas sensors for industrial and environmental applications.

■ ASSOCIATED CONTENT Supporting Information The details of the crystal structure determinations of [CdII 3 (H 2 O) 12 VIV 16 VV 2 O 36 (OH) 6 (AO 4 )]·24H 2 O (A= V, S), (1) have been deposited in CIF format. IR spectrum (KBr Pellet), Thermogram curve, experimental and simulated XRD pattern of 1. This information is available free of charge via the Internet at http://pubs.acs.org/.

■ AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]

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Crystalline Framework Material Containing Arrays of Vanadium Oxide Nanoclusters: A Polyoxovanadate Framework with Room Temperature NO x Sensing Properties M. Ishaque Khan, Naga Ravikanth Putrevu, Samar Ayesh, Elizabeth H. Yohannes, Brant Cage, Robert J. Doedens Polyoxovanadate based framework structure material [CdII 3 (H 2 O) 12 VIV 16 VV 2 O 36 (OH) 6 (AO 4 )]·24H 2 O (A= V, S), (1) which is composed of three-dimensional arrays of {V 18 O 42 (AO 4 )} nanoclusters, is a rare example of a new class of materials exhibiting interesting gas sensing properties promising for detecting environmentally detrimental NO x gases at room temperature.


Crystalline Framework Material Containing Arrays of Vanadium Oxide

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