Metal Coordination Polymer Framework Governed by Heat of

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A Metal Coordination Polymer Framework Governed by Heat of Hydration for Non-invasive Differentiation of Alkali Metal Series Shateesh Battu, Mahesh Itagi, Zahid Manzoor Bhat, Siddhi Khaire, Alagar Raja Kottaichamy, Lokesh Koodlur Sannegowda, Ravikumar Thimmappa, and Musthafa Ottakam Thotiyl Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b03541 • Publication Date (Web): 05 Oct 2018 Downloaded from http://pubs.acs.org on October 5, 2018

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Analytical Chemistry

A Metal Coordination Polymer Framework Governed by Heat of Hydration for Non-invasive Differentiation of Alkali Metal Series Shateesh Battu,1,# Mahesh Itagi,1,2,# Zahid Manzoor Bhat,1 Siddhi Khaire,1 Alagar Raja Kottaichamy,1 Lokesh Koodlur Sannegowda,2 Ravikumar Thimmappa,1 Musthafa Ottakam Thotiyl 1* 1

Department of Chemistry, Indian Institute of Science Education and Research, Dr. Homibhaba Road, Pune, India-411008 2 Department of Chemistry, VSK University Bellary, Karnataka, 583104 (India) *E-Mail: [email protected]

ABSTRACT: We illustrate that the extent of hydration and consequently the heat of hydration of alkali metal ions can be utilized to control their insertion/deinsertion chemistry in a redox active metal coordination polymer framework (CPF) electrode. The formal redox potential of CPF electrode for cation intercalation is inversely correlated to hydrated ionic radii, with clear distinction between the intercalation of ions across alkali metal series. This leads to non-invasive identification and differentiation of cations in the alkali metal series by utilizing a single sensing platform.

Metal ion sensing is extremely important in biological, environmental, industrial and energy applications.1-13 Simplicity and portability of electrochemical methodologies have conferred it with paramount significance in sensing research. Though coulometry and voltammetry are widely used electrochemical methods for electroanalysis; potentiometric techniques are particularly attractive as it is a non-destructive technique affecting the solution very little during the measurement.14-18 The indicator electrodes are often made selective to the analytes of interest such that the Nernstian voltage across the electrode/electrolyte interface depends strictly on the activity of the analyte. Though potentiometry is widely utilized for quantitative estimation, establishing the identity of various species across a sample series using the same sensing platform remain as an elusive challenge.6,14,17,19 We show that the redox energy required for insertion/deinsertion of metal ions in and out of a coordination polymer framework electrode belonging to Prussian blue analogue (PBA) can be controlled according to their extent of hydration, so as to achieve potentiometric differentiation of alkali

metal series using the same sensing platform. We demonstrate that interaction of the metal ions with the framework and its reversibility are largely influenced by the degree of hydration of alkali metal ions and consequently by their heat of hydration. Therefore, the electrode potential required for intercalation becomes more positive when the hydrated ionic radii (or the heat of hydration) decreases and vice versa. Experimental Section: Materials and Methods. Analytical grade sodium sulphate anhydrous (Na2SO4) (99%) and perchloric acid (HClO4) (70%) was procured from Fisher scientific, India and potassium ferricyanide (K3[Fe(CN)6]) (99%) was procured from Rankem, India. Nickel sulphate hexahydrate (NiSO4.6H2O) (99%) was procured from Alfa Aeasar, India. Analytical grade (>99%) metal nitrates MNO3 (M= Lithium, Sodium, Potassium and Cesium), NaCl, NaHCO3, KCl, KHSO4 and KHCO3 were procured from SD fine chemicals, India. Analytical grade RbNO3 was purchased from Sigma Aldrich, India.

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Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Na2Ni[Fe(CN)6] thin films (NiHCF) were electrochemically deposited on a glassy carbon electrode using a solution of 0.25 M Na2SO4 containing 0.5 mM K3[Fe(CN)6] and 0.5 mM NiSO4.6H2O by cycling the potential between 0.0 V to 0.85 V vs. Ag/AgCl/KCl (3 M) at a scan rate of 25 mV/s for 25 cycles.20,21 Pt mesh was used as the counter electrode. Electrochemical quartz crystal microbalance (EQCM) measurements were carried out using EG&G (QCM922A) by Au coated quartz crystal with a fundamental frequency of 8.95 MHz. Sauerbrey equation was used to find the mass of the deposited film by correlating the frequency shift to mass change.2 All the electrochemical experiments were performed in a typical three electrode setup using a Bio-Logic VMP-300 potentiostat. Electrode potentials were referred to an Ag/AgCl/KCl (3 M) reference electrode. A Pt wire was used as counter electrode. Cyclic voltammetry, EQCM measurements were performed using different electrolytes of MNO3 (where M= Li+, Na+, K+, Rb+, and Cs+) at various concentrations. The deposited thin films were characterized by various physico chemical techniques such as attenuated total reflection-Fourier transform infra-red (ATR-FTIR, Bruker Alpha), scanning electron microscopy (SEM) with energy dispersive X-ray spectrum (EDS) (Zeiss Ultraplus-4095), and Raman spectroscopy (LAB-RAM HR 800). X-ray diffraction (XRD) measurements were performed using Bruker D8 advance diffractometer. In order to calculate the detection limits, calibration plots were constructed between the open circuit voltage (OCV) and concentrations of cations. OCV was measured by taking the average value of voltage for a given concentration of a cation in three different measurements. By taking the linear fit of the data at lower concentration for each metal ion, the slopes and sensitivities were extracted. The limit of detection (LOD) for each metal ion was calculated by assuming a signal to noise ratio of 3 using equation 1. 𝒔𝒕𝒂𝒏𝒅𝒂𝒓𝒅 𝒅𝒆𝒗𝒊𝒂𝒕𝒊𝒐𝒏 𝑳𝑶𝑫 = 𝟑  (1) 𝒔𝒍𝒐𝒑𝒆 Device Fabrication A home-made cation sensor for potentiometric discretion was fabricated using NiHCF modified electrode as sensing probe and Ag/AgCl (3 M KCl) as the non-polarizable interface. The voltage developed across this two electrode system was correlated to the nature and concentration of cations in the analyte solution. The voltage across the

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cell varied from 0.2 V to 0.5 V according to the cation and its concentration. The individual voltages of cation do not overlap with other for concentrations ranging from 1 mM to 10 mM. These voltages for various metal ions were given to an Arduino Uno board based on microcontroller Atmega 328. The obtained instantaneous voltages from the analyte solutions were compared with the voltage ranges for each cation and the results were displayed on the 20*4 Alphanumeric Liquid Crystal Display. The block diagram, hardware and flow chart of cation sensor are provided in Figure S1, supporting information. Results and discussion: Na2Ni[Fe(CN)6] or NiHCF film coated glassy carbon electrode was prepared by repetitive cyclic voltammetry using a solution of 0.25 M Na2SO4 containing 0.5 mM K3[Fe(CN)6] and 0.5 mM NiSO4.6H2O, 20,21 Figure 1a. Appearance of redox features and their concomitant growth during repetitive cyclic voltammetry signals a growing film encompassing redox active metal ions. The amount of NiHCF deposited on the electrode is determined from electrochemical quartz crystal microbalance (EQCM) studies, suggesting a mass change of 5.5 μg after 25 cycles of deposition process, inset of Figure 1a. Scanning electron microscopy (SEM) with energy dispersive X-ray spectrum (EDS) suggest nearly uniform coating and the presence of Na, Ni, Fe, C and N as part of the film, Figure S2 supporting information. Fourier transform infrared (FTIR) spectrum of as deposited film, Figure 1b, demonstrates vibrations at 2072 cm-1 which are assigned to -CN ligand bridged to Fe (II) ions.22,23 Raman spectra shows representative peaks close to 2072, 2152 and 2328 cm-1 which are characteristics for Na2NiFe(CN)6,24 Figure S3, supporting information. X-ray diffraction pattern (Figure S4, Supporting Information) demonstrates the formation of Na2Ni[Fe(CN)6] in accordance with the literature.25,26 All these points to the formation of Prussian blue analogue of the formula Na2Ni[Fe(CN)6] during electrochemical deposition by the reaction shown in the equation 2.27,28 (𝑰𝑰)

𝟑−

(𝑰𝑰𝑰) (𝑪𝑵)𝟔 ](𝒂𝒒) 𝟐𝑵𝒂+ (𝒂𝒒) + 𝑵𝒊(𝒂𝒒) + [𝑭𝒆

→ 𝑵𝒂𝟐 𝑵𝒊[𝑭𝒆(𝑰𝑰) (𝑪𝑵)𝟔 ]

(𝟐)

UV-Vis spectroelectrochemistry of the film, Figure 1c and Figure 1d demonstrate an increase and a


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(a)

(b)

stretching

(c)

(d)

Figure 1. (a) Cyclic voltammogram obtained at a scan rate of 25 mV/s during the electrochemical deposition of NiHCF film using a solution of 0.25 M Na2SO4 containing 0.5 mM K3[Fe (CN)6] and 0.5 mM NiSO4.6H2O. Inset shows the mass gain (extracted from EQCM) during the film formation. (b) FTIR spectrum of as deposited film on a carbon electrode. UV-Vis spectroelectrochemistry during (c) oxidative and (d) reductive polarization scans. decrease in absorbance near 400 nm during positive shift in the formal potentials is evident in the tive going scan and negative going scan respectivevoltammogram on going down the alkali metal sely, cyclic voltammogram, Figure S5, Supporting Inries from Li to Cs, Figure 2a with Cs ion appearing formation. The absorption peak close to 400 nm at more positive potentials and Li ion appearing at more negative potentials. Based on their ionic radii corresponds to charge transfer transition in Fe3+ in the periodic table, Cs ion insertion should occur species in NaNi[Fe(CN)6].29,30 These indicate that at more negative potentials, however the trend in the electrochemistry of Fe2+ ions are responsible for their redox behavior, Figure S5, supporting informal potentials are found to be inverse to this formation.31,32 This redox transition of transition expectation, Figure 2a and Figure 2b. This anomaly however can be explained by the hydrated ionic metal ion is accompanied by insertion/deinsertion radii and consequently by their heat of hydration. of alkali metal ions for charge balance as shown in As the electrode is intercalation type, a disparity in equation 3. the redox energy required for metal ion inser𝑵𝒂𝟐 𝑵𝒊(𝑰𝑰) [𝑭𝒆(𝑰𝑰) (𝑪𝑵)𝟔 ] ⇔ (𝑰𝑰) (𝑰𝑰𝑰) + − tion/deinsertion in and out of the NiHCF electrode (𝑪𝑵)𝟔 ] + 𝑵𝒂 + 𝟏𝒆 … … . (𝟑) 𝑵𝒂𝑵𝒊 [𝑭𝒆 can be anticipated based on their ionic radii. On Equation 3 points to the fact that the elecmoving down the alkali metal series, the ionic radii trochemistry of NiHCF should be sensitive to the increase, consequently the extent of hydration and nature of the alkali metal ion in electrolytic soluthe heat of hydration should follow a reverse tion, cyclic voltammogram, Figure 2a. A clear posi-



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Alkali metal ions

(a)

(b)

(c)

(d)

Figure 2. (a) Cyclic voltammograms of NiHCF electrode at a scan rate of 25 mV/s in 0.25 M aqueous solutions of MNO3 (M= Li, Na, K, Rb and Cs). (b) Formal potentials as a function of the alkali metal cation radii and their hydration energies, (values are taken from references 29 and 30), (c) typical cyclic voltammograms obtained on successive addition of 10 mM MNO3 (M= Na, K, Rb and Cs) to 10 mM LiNO3 solutions at 25 mV/s scan rate, and (d) the corresponding shift in their open circuit potentials (OCV). trend,33,34 Figure 2b. Therefore, hydrated ionic radii (and heat of hydration) of alkali metal cations decrease on going down the alkali metal series, explaining the shift in formal potential towards more positive potential when moving from Li+ to Cs+, Figure 2a. Reaffirming this, the formal potentials of NiHCF electrode in LiNO3 solution builds up positively when the solution is successively incremented with metal ions in the alkali metal series in chronological order of their atomic number, cyclic voltammograms, Figure 2c. This is further clear from the open circuit potential (OCV) vs. time plots when the solution is successively injected with MNO3 (where M is alkali metal cation) in chronological order of their atomic number, Figure 2d. These demonstrate that the sensing architecture is governed by hydrated ionic radii or by heat of hydration of alkali metal ions leading to their poten-

tiometric or non-invasive differentiation. It should be noted that, formal potential shift between two electrolyte solutions in the cyclic voltammograms, Figure 2c, is commensurate to their OCV shifts, Figure 2d. The formal potentials in Figure 2b are extracted using fresh solutions and electrodes (Figure 2a) and OCVs in Figure 2d are obtained on successive addition of MNO3 (where M = Na, K, Rb and Cs) to LiNO3 solution. This coupled with their different concentration may be responsible for the difference between the formal potentials in Figure 2a-2b and OCVs in Figure 2d. Nevertheless, NIHCF film can take up cations in alkali metal series which is further confirmed by FTIR spectroscopy and SEM with EDS, Figure S6 and S7 supporting information. Taken together, the data in Figure 2 clearly demonstrate that by the extent of hydration of alkali metal cations control their redox chemis-


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try in the CPF electrode and consequently larger cations in the alkali metal series can be intercalated easily compared to smaller cations. Therefore, we do not claim that individual components in a mixture of metal ions can be identified by this NiHCF sensor because the sensor output in the mixture will be dominated by the metal ion which can be intercalated easily (Figure 2c and Figure 2d). Consequently, in a mixture of alkali metal ions as in Figures 2c and 2d, the smaller cations in the film will be replaced by the larger ones. It is because of this reason that with a mixture of alkali metal cations containing Li+, Na+, K+, Rb+ and Cs+, the larger Cs+ ion response dominates the cyclic voltammogram, Figure 2c. Combined OCV and QCM data, Figure 3a and Table S1, supporting information suggest that

the OCV scale up on successive addition of MNO3 in chronological order of their atomic number which is commensurable with the mass change in the QCM. The voltammogram (Figure S8, supporting information) and corresponding EQCM signals, Figure 3b and 3c, when the electrolyte is switched from Li ion solution to Cs ion solution through Na, K, and Rb ion solutions, demonstrate a clear increment in mass on moving down the alkali metal series. Figure 3b and 3c further show that there are mass changes during oxidation and reduction scans suggesting respectively deintercalation and intercalation of cations. To confirm the processes at oxidation and reduction potentials unambiguously, we held the potentials at respective potentials (for e.g., in RbNO3 solution) and recorded the current and frequency responses simultaneously,

Figure 3. (a) OCV profiles in combination with QCM mass profiles for NiHCF film on adding 10 mM MNO3 (M= Na, K, Rb, Cs) in chronological order of their atomic number to 10 mM LiNO 3 solution. (b) The EQCM profiles during cyclic voltammograms at 5 mV/s scan rate and (c) the corresponding mass change during oxidation and reduction for cations in alkali metal series. (d) Chronoamperometry in combination with



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EQCM for NiHCF electrode in 10 mM RbNO3 electrolyte. Potential is held at oxidation (0.9 V) and reduction (-0.3 V) potentials and frequency and current are monitored as a function of time. Figure 3d. The frequency increased during oxidation process and decreased during reduction process confirming the de-intercalation and intercalation of cations respectively. To confirm the absence of anionic effect on formal potential and OCV shifts, we have carried out control experiments with the same cation however with different anions, Figure S9 (Supporting Information), depicting only a marginal shift in redox potential with respect to different anions in electrolyte solution. Taken together, the coordination polymer framework of Prussian blue analogue respond to alkali metal ions in tune with their hydration energy in such a way that metal ions with lower hydration energy can be intercalated easily and vice versa. This can be exploited to achieve potentiometric discretion of metal ions in alkali metal series as demonstrated below. OCVs for different concentrations of cations in the alkali metal series and the corresponding calibration plots, Figure 4a, suggest that each metal ion follow distinct voltage profiles leading to their differentiation in the series. Though the detection limits and sensitivity varies (extracted from the low concentration region) for each metal ion varies (Table 1), the strategy opens up a platform for discretion of alkali metal series as each metal ion maintains a distinct voltage at any given concentration. At higher concentrations (beyond 2 mM) their signals demonstrate a lower slope with tendencies for saturation however; each metal ion still maintains a distinct voltage profile, Figure 4a.

As demonstrated in Table 1, the sensitivities vary across the alkali metal series without any trend across the alkali metal series. At the moment, we do not have an answer for the lack of trend in sensitives and we believe it has something to do with the type of interaction the individual metal ions experience with the CPF lattice. Nevertheless, successive detection of different metal ions using the same sensing platform is possible as one goes from Li+ to Cs+, however the reverse (Cs+ to Li+) is not feasible perhaps due to the strong affinity of Cs to NiHCF. It is observed that Cs ion intercalated electrode can be regenerated using HClO4 treatments for 30 minutes which may be due to the strong oxidizing action of perchlorate anion,35 Figure S10a, supporting information. Such an electrode could be recycled with similar response in different alkali metal ion solutions demonstrating extended cyclability by chemical treatments, Figure 4b, Figure S10b and Figure S10c, Supporting Information. Chemical regeneration is further supported by SEM with EDS analysis, Figure S11, Supporting Information, demonstrating extended cyclability with the same sensing platform. We have fabricated a home-made sensor which is capable of potentiometric discerning of different alkali metal ions and accompanying video demonstrates its feasibility (Video 1). The sensing architecture consists of NiHCF electrode as the working electrode and an Ag/AgCl/KCl (3 M) as the non-polarizable interface.

Table 1: Electrochemical and sensing parameters of CPF electrode for the alkali metal cations in combination with their heat of hydration and ionic radii.

a ,b

MNO3

Formal potential (V)

Ionic radii (a) (pm)

ΔHhyd(b) (kJmol-1)

Sensitivity(c) (mV/mM)

LOD (mol)

LiNO3 NaNO3 KNO3

0.127 0.355 0.477

76 102 138

-519 -406 -322

26.5 18.4 26.4

2.6*10-7 5.0*10-7 5.2*10-7

RbNO3

0.634

152

-293

32.4

5.4*10-7

CsNO3

0.752

167

-264

22.6

3.9*10-7

Values are according to the references 33 and 34. c At lower concentration regime.


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Figure 4. (a) OCVs as a function of concentrations of MNO3 (M= Li, Na, K, Rb and Cs) and (b) cyclic voltammograms at 25 mV/s scan rate with freshly prepared and HClO4 reactivated NiHCF film in MNO3 (M= Li, Na, K, Rb and Cs) solutions in chronological order of their atomic number. Conclusion: We have demonstrated non-invasive differentiation of alkali metal series by utilizing the Nernstian voltage dependence of CPF electrode to the heat of hydration of alkali metal ions. The distinct redox potentials governed by their extent of hydration allowed control over their insertion/deinsertion redox energies, leading to a noninvasive electrochemical sensor with decent precision for distinguishing alkali metal ions.

The supporting information contains Figure S1S11 and Table S1. The Supporting Information is available free of charge on the ACS Publications website.

*E-Mail: [email protected]

Department of Chemistry, Indian Institute of Science Education and Research, Dr. Homibhaba Road, Pune, India-411008 # indicated authors contributed equally

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Metal Coordination Polymer Framework Governed by Heat of

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