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A Zinc Battery Driven by an Electro-organic Reactor Cathode Mahesh Itagi, Shateesh Battu, Mruthyunjayachari Chattanahalli Devendrachari, Zahid Manzoor Bhat, Alagar Raja Kottaichamy, Deepraj Pandit, Manu Gautam, Ravikumar Thimmappa, Lokesh Koodlur Sannegowda, and Musthafa Ottakam Thotiyl ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03486 • Publication Date (Web): 20 Sep 2018 Downloaded from http://pubs.acs.org on September 20, 2018

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ACS Sustainable Chemistry & Engineering

A Zinc Battery Driven by an Electro-organic Reactor Cathode Mahesh Itagi ‡ a,b, Shateesh Battu

‡a

, Mruthyunjayachari Chattanahalli Devendrachari a, Zahid

M. Bhata, Alagar Raja Kottaichamy a, Deepraj Pandita, Manu Gautama, Ravikumar Thimmappa a, Lokesh Koodlur Sannegowda b, Musthafa Ottakam Thotiyl a,*

a

Department of Chemistry and Center for Energy Science, Indian Institute of Science Education

and Research Pune, Dr Homi Bhabha road, Pashan, Pune, India -411008. b

Department of Chemistry, VSK University Bellary, Karnataka, 583104 (India)

*Email: [email protected]

ABSTRACT Synthesis of organic molecules by utilizing the principles of electrochemistry satisfies 9 out of the 12 postulates of green chemistry, conferring electrochemical synthetic methodologies with clean, safe and green tags. However, electro-organic synthesis is a heterogeneous interfacial reaction demanding significant driving force in terms of voltage or current. Here we demonstrate an unusual route for electro-organic synthesis during electricity generation in a battery, where the positive half-cell is designed to function as an organic reactor generating useful chemicals and fuels during power production. The proposed electro-organic synthesizer Zn battery couples power production with the synthesis of extremely useful chemicals such as aromatic amines and fuel such as alcohols

ACS Paragon Plus Environment

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during the discharge chemistry, demonstrating its tremendous potential in the sustainable energy landscape. KEYWORDS: Electro-organic Synthesis, Zinc Battery; Electrocatalysis; Green Chemistry

INTRODUCTION Electro-organic synthesis by using the principles of electrochemistry is considered as a clean and a safe synthetic strategy as it satisfies majority of the postulates of green chemistry.1-3 The ability to control the reaction by simply modulating the applied voltage, the opportunities for performing the reaction at room temperature and in green solvents coupled with its ability to generate reactive species under mild conditions confer electrochemistry with a green tag.4-7 However, electro-organic synthesis is a heterogeneous interfacial reaction often demanding significant input voltage for driving the reaction at the rate required,8,9 and there are enormous efforts across the globe to invent new catalyst/catalyst combination to substantially bring down the overvoltage.10,11 It will be a distinct progress in the domain of electro-organic synthesis if it can be accomplished during power production, for example in batteries and fuel cells. State of the art batteries convert the chemical energy of assembled components into electricity during power production.12-17 The electrons generated at the anode usually cause a reduction reaction either within the cathode, or at the interface.18-20 For example, in Li ion batteries, the electrons often cause a reduction within the cathode with simultaneous Li ion intercalation.21-24 In metal air batteries and fuel cells, the electrons are captured by oxygen having positive redox energy at the interface.25-27 Here we show an unusual primary battery concept, wherein the electrons released by the anode are driven to cause a reductive organic reaction thereby the cathode functions as an organic reactor. The proposed electro-organic synthesizer Zn battery simultaneously enables


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power production with the synthesis of extremely useful chemicals such as aromatic amines and fuel such as alcohols during the discharge chemistry, demonstrating its tremendous potential in the sustainable energy landscape.

EXPERIMENTAL SECTION Materials and Methods HCl (99.99%), H2SO4 (99.99%), NaCl (99.99%), Na2SO4 (99.99%), NaNO2 (99.99%), NaOH (97%), CDCl3 (99.9), isopropyl alcohol (99.7), β-naphthol (98%), aniline (99.5%), oxalic acid (99%), glycolic acid (99%), ethyl acetate (99.99%), 2,7-dihydroxynaphthalene (99%) and nitrobenzene (99%) were of analytical grade and were procured from Sigma Aldrich, India. Ketjen black carbon was procured from Sigma Aldrich, India. Zinc and lead foil was procured from Alfa Aesar. All the electrochemical experiments were performed with, Biologic VMP 300 electrochemical workstation. Cyclic voltammograms for the nitrobenzene were collected at different scan rates in three electrode system with a glassy carbon (GC) electrode as the working electrode in different concentrations of nitrobenzene dissolved in equal volumes of 0.25 M H2SO4 and isopropyl alcohol. A Pt mesh and Ag/AgCl (3 M KCl) were used as the counter and reference electrodes respectively. Deposition and stripping of Zn studies were carried out in 0.5 M potassium hydroxide solution. Rotating disk electrode (RDE) measurements were carried out (PARSTAT MC, AMETEK) in nitrogen purged solution of nitrobenzene (5 mM) dissolved in equal volumes of isopropyl alcohol and 0.25 M H2SO4 at a scan rate of 5 mV/s at different rotations per minute (100, 300, 500, 700, 900, 1100). The experimental data were analyzed with the help of Koutecky-Levich equation (1) to estimate the number of electrons at different potentials using the equation 1.


3


1 𝑖

=

1 𝑖𝑘

+

1 0.620 𝑛 𝐹

𝐴 𝐷 2⁄3

1 𝜈 − ⁄6 𝐶 𝜔 1⁄2

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(1)

Where i - disk current, ik - kinetic current, n - number of electrons, F - faradays constant (96485 C mol-1), A - area of electrode (cm2), D - diffusion coefficient (cm2 s-1), ʋ - kinematic viscosity (cm2 s-1), C - concentration (mol cm-3) and ω - rotational speed (rad s-1). Zn-nitrobenzene battery was constructed in a home-made two compartment cell by dipping a zinc electrode in 2 M KOH as anodic half-cell and a carbon electrode (Ketjen black carbon coated on Toray carbon paper at a loading of 3 mg/cm2) in equal volumes of isopropyl alcohol and 2 M sulfuric acid containing 0.2 M nitrobenzene as cathodic half-cell. Zn-oxalic acid battery architecture consists of a zinc electrode dipped in 6 M KOH as anodic half-cell and a lead (Pb) electrode immersed in 2 M sulfuric acid containing 0.7 M oxalic acid as cathodic half-cell. Anodic and cathodic half cells were separated by a Nafion 117 membrane in both the cases. Characterization Discharge product from the Zn-nitrobenzene battery was extracted by the following procedure. It was taken in a separating funnel. The discharged product contains both aniline (in the soluble form as anilinium ion) and unreacted nitrobenzene as separate layers. The nitrobenzene was extracted and separated using ethyl acetate and anilinium ion remained in the aqueous layer. The acidic aqueous layer was neutralized by sodium hydroxide followed by the addition of sodium chloride to convert anilinium ion into aniline which forms an oily layer on the aqueous phase. This aniline oily layer was extracted and washed thoroughly with ethyl acetate and then the solvent was evaporated using a rotary evaporator. Finally, obtained product was stored in an air tight container for further analysis. Discharged product from Zn-oxalic acid battery was extracted similarly using ethyl acetate in a separating funnel. The organic layer containing the discharge product was


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allowed to evaporate at room temperature. The product was recrystallized from ethyl acetate 3 times to remove the foreign particles and impurities. UV-Visible measurements of discharge products were carried out in a quartz cuvette using a Perkin Elmer Lambda 950 instrument. Absorbance of azo dye obtained by the reaction of Znnitrobenzene battery discharge product with β-Naphthol was measured in comparison of their azo dye from standard aniline and standard nitrobenzene in the UV-vis region. For the Zn-OA battery, the formation of glycolic acid during the discharge chemistry was followed by colorimetric test with 2,7-dihydroxynaphthalene in conc. H2SO4 medium. Briefly, the formaldehyde formed by the reaction of glycolic acid with concentrated sulfuric acid at 100C react with 2,7dihydroxynaphthalene to produce 2,2',7,7'-tetrahydroxy-1,1'-dinaphthylmethane. Its further oxidization to quinoidal compound results in a deep red-violet color with a characteristic absorption peak around 540 nm in UV-visible spectroscopy.28,29 FTIR spectra of battery discharge products were compared with standards such as aniline, nitrobenzene, oxalic acid and glycolic acid using a Bruker Alpha ATR-FTIR. Nuclear magnetic resonance (NMR) spectra were recorded with Bruker 400 MHz spectrometer and high resolution mass spectrometry (HRMS) were recorded with Waterssynapt G2. Scanning electron microscopy (SEM) with energy dispersive X-ray spectrum (EDS) were carried with Zeiss Ultraplus-4095 instrument. X-ray diffraction measurements were performed using Bruker D8 advance diffractometer. Expected amount of discharge product was calculated during galvanostatic polarization using equation 2. 𝑀𝐼𝑡 𝑛𝐹

(2)


5


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Where, M- molecular mass of discharge product, I – discharge current, t-time, F-Faraday constant (96485 C mol-1) and n is the total number of electrons required for the conversion. Expected percentage yield of product was calculated using equation 3. 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑 𝑏𝑎𝑠𝑒𝑑 𝑜𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑓𝑙𝑜𝑤 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑 𝑜𝑛 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛

𝑋 100

(3)

The current efficiency (CE) for anticipated product was calculated using equation 4.

CE=

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑐𝑎𝑡ℎ𝑜𝑙𝑦𝑡𝑒 𝑎𝑓𝑡𝑒𝑟 𝑏𝑎𝑡𝑡𝑒𝑟𝑦 𝑑𝑖𝑠𝑐ℎ𝑎𝑟𝑔𝑒 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑 𝑏𝑎𝑠𝑒𝑑 𝑜𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑓𝑙𝑜𝑤

𝑋 100

(4)

RESULTS AND DISCUSSION

Scheme 1. Scheme of the electro-organic synthesizer battery. The battery architecture is shown in scheme 1 and it consists of a Zn metal anode housed in alkaline medium and a carbon or a Pb electrode housed in an acidic medium containing organic molecules as electron acceptors. The anodic and cathodic half cells are separated by an ion exchange membrane (Nafion 117). For the Zn-nitrobenzene (NB) battery, Zn electrode housed in 2 M KOH solution is utilized as anodic half-cell and a carbon electrode immersed in equal volumes


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of isopropyl alcohol and 2 M H2SO4 containing 0. 2 M NB is employed as cathodic half-cell. Alkaline medium is chosen for Zn anodes due to the well-known stability of Zn electrode with respect to hydrogen evolution reaction (HER) in basic pH.30-32 The cyclic voltammogram of a glassy carbon electrode in an alkaline medium containing Zn ions demonstrates deposition and stripping of Zn in the negative potential range, Figure S1a, Supporting Information. Protonation of aromatic nitro compounds require an acidic medium, justifying the use of acidic environment to house the oxidant.33,34 Further, conversion of aromatic nitro compounds to corresponding amino compounds are multi-electron multi-step processes, which can be catalyzed by carbon based electrodes, Au and Pt electrodes.35-37 Carbon electrode was found to be an effective candidate for hydrogenation of nitro compounds, Figure S1b, Supporting Information, with faradaic peaks appearing at less negative potentials compared to Zn stripping/deposition, Figure S1a, Supporting Information. The nitrobenzene (NB) reduction peak current is found to increase linearly with respect to the concentration and a plot of log (i) vs. log (scan rate, ) demonstrated a slope of 0.5, Figure S1c and Figure S1d, Supporting Information. According to Randles-Sevicik equation,38,39 for a diffusion-controlled reaction peak current is directly proportional to 1/2, consequently a logarithmic plot between the two should yield a slope of 0.5. Therefore, the data in Figure S1d suggest a diffusion controlled interfacial process. The rotating disk electrode studies on a carbon disk electrode at different rotation speeds are shown in Figure S2a (Supporting Information), and the corresponding Koutecky-Levich plot demonstrates the numbers of electrons transferred are 6 at applied potential close to -0.58 V vs. SHE, Figure S2b (Supporting Information). It should be noted that the number of electrons vary with respect to the potential applied (Table S1, Supporting Information) indicating the multiple pathways possible during the reduction of NB.40,41 These evidence that carbon is efficient for the


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multi-electron reduction of nitrobenzene to aniline as shown in equation 5. As explained earlier, the electrochemical conversion of nitrobenzene is a multi-electron multistep process and the complete conversion of nitrobenzene to aromatic amine involves 6 electrons. There are various elementary steps (Scheme S1, supporting information) which involve the formation of nitrosobenzene, N-hydroxyaniline etc., prior to the formation of aromatic amines.42,43 Therefore, the process exhibits sluggish electrode kinetics which is primarily responsible for a sloping limiting current during rotating disk electrode analysis.

The single electrode potentials of Zn in alkaline medium and carbon electrode in 0.2 M NB solution in equal volumes of isopropyl alcohol and 2 M H2SO4 and, Figure 1a, shows that NB is positioned at positive redox energy relative to Zn/Zn2+, making NB an electron acceptor for the electrons released by Zn electrode, equations 6 and 7. This suggest that total cell reaction involves the oxidation of Zn to Zn2+ ions and the electro-organic synthesis of aromatic amines by the reduction of NB, equation 8. The polarization curve of Zn-organic reactor battery, Figure 1b (green trace), demonstrates an open circuit voltage of 1.5 V, a peak power density of 125 mW/cm2 at a peak current density of 195 mA/cm2. The polarization curve without NB (blue trace in Figure 1b) demonstrated a power density of only 33 mW/cm2 at a peak current density of 95 mA/cm2 which is typical of a Zn-carbon battery.44-46 The galvanostatic polarization of Zn-NB organic reactor battery at different current densities, Figure 1c, indicates a decline in cell voltage when the current rating is increased which is typical of a battery. At any given current it is usual that a battery experiences activation, ohmic and concentration polarizations which will become severe at higher


8

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current ratings.47,48 These are responsible for the voltage drops at higher current ratings in Figure 1c. Since the battery resembles a hybrid redox flow architecture, we have normalized the capacity with respect to the volume of the cathodic solution, Figure S3, Supporting Information. The volumetric capacity at lower current rating is close to 10 Ah/L and this marginal figure of merit is attributed to limited solubility, sluggish electrode kinetics and mass transport limitations of NB. The individual electrode polarizations, Figure 1d, suggests that the cathode limit the overall reaction which is apparent given the multi-electron multi step nature of the cathodic process (Scheme S1, supporting information) and limited solubility of nitrobenzene (0.2 M) in the electrolyte medium. Theoretical discharge capacity (gravimetric) of Zn-NB battery is 1306.75 mAh/g with respect to nitrobenzene, however the experimental capacity is close to 425 mAh/g (at 20 mA/cm2 in Figure 1c). As explained above, the decrease in discharge capacity with respect to theoretical discharge capacity should be due to electron and mass transport limitations of NB at the battery cathode. Anode: 𝑍𝑛2+ + 2ⅇ − → 𝑍𝑛

ESHE = -1.15 V

(6)

ESHE = 0.40 V

(7)

Ecell = 1.55 V

(8)

Cathode: 𝐶6 𝐻5 𝑁𝑂2 + 6𝐻 + + 6ⅇ − → 2𝐻2 0 + 𝐶6 𝐻5 𝑁𝐻2 Total cell reaction: 3𝑍𝑛 + 𝐶6 𝐻5 𝑁𝑂2 + 6𝐻 + → 3𝑍𝑛2+ + 2𝐻2 0 + 𝐶6 𝐻5 𝑁𝐻2


9


(a)

(b)

(c)

(d)

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Figure 1. (a) Single electrode potentials of Zn anode in 2 M KOH and carbon electrode in equal volumes of isopropanol and 2 M H2SO4 and containing 0.2 M NB. (b) Polarization curves of Znorganic reactor battery with and without NB. (c) Discharge curves of the Zn-NB organic reactor battery at different current rates and (d) cathodic and anodic half-cell polarization curves. The cathodic compartment reaction of Zn-NB battery is investigated by various spectroscopic techniques after long term polarization. The products obtained from the battery are confirmed to be aromatic amines by simple color tests based on diazonium salts and also from other techniques. The products from the battery after extraction and purification (see experimental


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section for more details) are made to react with nitrous acid to form diazonium salts which are then coupled with β-naphthol to form orange colored azo dye, Figure 2a. This colour test is negative with the starting compound NB and positive with standard aniline and the products obtained from the battery cathode, suggesting the conversion of aromatic nitro compounds to corresponding aromatic amines in the battery. The obtained colored azo dye was dissolved in chloroform and then characterized by UV-vis spectroscopy, Figure 2b. The characteristic absorption peak of azo bond was observed as a broad band at 482 nm.49-52 This indicates the presence of aromatic primary amines as the main product in the battery discharged product; otherwise the azo dye formation by reaction with β-naphthol (Figure 2c) would not be possible. For standard NB and β-naphthol mixture, no obvious peaks are observed around 482 nm and 260 nm corresponding to azo bonds and aromatic amines respectively. These evidence the conversion of nitrobenzene to aromatic primary amines in the battery during power generation. The thin layer chromatography spotting was done in order to monitor the progress of the reaction and to confirm the purity level of the products obtained. The retention factors (Rf) for standard NB and standard aniline in nhexane/ethyl acetate solvent system are 0.70 and 0.40 respectively. For the product obtained from the battery, the Rf value is found to match well with that of standard aniline, Figure S4, Supporting Information. This indicates the conversion of NB to aniline.


11


(a)

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(b)

(c)

Azo Bond

Figure 2. (a) Azo dye formation tests for aromatic primary amines and (b) UV-vis spectra of obtained azo dyes. (1) With standard NB, (2) with standard aniline and (3) with the discharge product obtained from the battery cathode. (c) Reaction scheme for azo dye formation by the reaction of aromatic primary amines with β-naphthol. In the discharge product obtained from the battery cathode of Zn-NB battery, vibrational peaks in the Fourier transform infra-red spectra (FTIR) at 3432 cm-1 and 3390 cm-1 (N-H stretching peaks) are characteristics of amine functional groups, Figure 3a. The compound before discharge in battery resembled that of NB with its characteristic vibrations at 1524 cm-1 and 1347 cm-1 (N=O stretching vibrations), Figure 3a. 1H NMR (400 MHz, CDCl3) of standard aniline demonstrate chemical shifts at δ 3.45 (s, 2H), 6.70-6.72 (d, 2H), 6.73-6.82 (dd, 1H), and 7.17-7.22 (t, 2H), and standard NB demonstrate chemical shifts at 7.54-7.59 (t, 2H), 7.74-7.70 (dd, 1H) and 8.23-8.27


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(d, 2H), Figure 3b. The products from the battery cathode demonstrate chemical shifts at δ 3.43 (s, 2H), 6.71-6.72 (d, 2H), 6.73-6.82 (dd, 1H), 7.17-7.22 (t, 2H) suggesting the formation of aniline, Figure 3b. High resolution mass spectroscopy (HRMS) of the product obtained from the battery cathode, Figure 3c, demonstrate the presence of an intense peak at 94.13 corresponding to parent ion of aniline. The peaks at 118 correspond to sodium adduct of aniline53 formed during the extraction process (see experimental section for more details) and the peak at 77 correspond to the fragment of aniline, Figure 3c. This unambiguously confirms the conversion of nitrobenzene to aromatic amines in the battery during the discharge chemistry. Taken together, NMR, FTIR and mass spectrometry, clearly demonstrate the formation of aromatic amines during the discharge of the battery. Further, the product obtained from the battery can be electrochemically polymerized to form polyaniline (PANI) which is clear from the growth of faradic peaks during repetitive cyclic voltammetry, Figure 3d. The faradaic peaks in Figure 3d in the voltammogram correspond to the conversion of lucoemeraldine base (EB) to emeraldine salt (ES) and emeraldine salt to pernigraniline (PG) in the positive going scan, and their switching back in the negative going scan which are characteristics for PANI.54,55 The starting compound (nitrobenzene) under identical conditions, did not demonstrate any signatures of electrochemical polymerization, Figure S5, Supporting Information. This clearly indicates the conversion of nitro to amine compound in the battery during power generation. Based on the number of electrons (6 electrons) transferred during the organic reaction (equation 5), the theoretical percentage of conversion is estimated to be 32% (calculation S1, supporting information), and the lower turnout are attributed mainly to concentration polarization and mass transport limitation. Therefore, by increasing the mass transport by forced convection or by continuously flowing the catholyte using a peristaltic pump, it should be possible to increase the yield well beyond this point. As these reactions are interfacial,


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another strategy which can further increase the yield is to utilize sponge type electrodes with large reaction surface area. The weight of aromatic amines obtained after the battery discharge is 0.115 g, (calculation S1, Supporting Information), therefore, the current efficiency (CE) for the conversion of NB to corresponding aromatic amines is close to 97% (calculation S1, supporting information) indicating negligible occurrence of parasitic chemistry at the cathode of Zn-NB organic reactor battery. The stability of anodic and cathodic interfaces during long term polarization were investigated by SEM with EDS and XRD techniques. SEM with EDS of Zn anode, Figure S6, Supporting Information, demonstrate clearly the etching and surface oxidation of Zn electrode during the discharge chemistry (Figure S6a, S6b, Supporting Information). The significant contribution of oxygen in the EDS pattern of the Zn electrode after long term polarization (Figure S6c and S6d, Supporting Information) suggest oxide formation in alkaline medium which is supported by the XRD pattern, Figure S7, Supporting Information. The observation of potassium signal in the EDS pattern after long term polarization (Figure S6d, Supporting Information) may be due to the adsorption of zincate on the electrode surface. The carbon electrode demonstrate a noticeable change in surface roughness after long term polarization, SEM image, Figure S8a and S8b, Supporting Information, which may partly be due to the adsorption/deposition of discharge product, EDS pattern, Figure S8c and S8d, Supporting Information. However, a structural change for carbon electrode is ruled out as the XRD pattern for used carbon remain unchanged even after long term polarization (Figure S9, Supporting Information). All these demonstrate that the interfaces are sufficiently stable and Zn-NB organic reactor battery is capable of generating an output power along with the synthesis of extremely useful aromatic amines from corresponding nitro compounds during the discharge chemistry.


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(a)

(b)

O M P CDCl3 Standard NB

M O P Standard aniline

M O Discharge Product P

(c)

(d)

MW=93.13

Figure 3. (a) FTIR spectra and (b) 1H nuclear magnetic resonance (1H-NMR) spectroscopy (400 MHz) of standard NB, standard aniline and the product obtained from the battery cathode during the discharge chemistry. (c) High Resolution Mass Spectrometry (HRMS) of the product obtained from the battery cathode during the discharge and (d) cyclic voltammogram at a scan rate of 20 mV/s during the electrochemical polymerization of the product obtained from the Zn-NB organic reactor battery cathode. EB is lucoemeraldine, ES is emeraldine salt and PG is pernigraniline forms of polyaniline. We further demonstrate that proposed Zn-organic reactor battery can be utilized for fuel synthesis and we establish it by converting oxalic acid (OA) to glycolic acid (an alcohol) in the


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cathode by exploiting the electrocatalytic reduction of -COOH functionalities to alcoholic compounds. It is well known that alcohols are safer energy carrier molecules and consequently; their production in batteries during electricity generation will be a distinct progress in the sustainable energy landscape.56,57 The proposed Zn-fuel synthesizer battery consists of a Zn anode housed in 6 M KOH as the anodic half-cell and a Pb electrode dipped 2 M H2SO4 containing 0.7 M OA as the cathodic half-cell. Pb electrode was chosen as the cathodic electrocatalyst because of its electrocatalytic ability to reduce OA to alcoholic compounds.58,59 The single electrode potentials of Zn electrode in alkaline medium (6 M KOH) and Pb electrode in acidified OA solution (0.7 M OA in 2 M H2SO4), Figure 4a, indicate that OA can be an electron acceptor on a Pb cathode in the proposed Zn-organic reactor battery. The polarization curve of Zn-OA battery, Figure 4b (orange trace), demonstrates an open circuit voltage of 1.07 V, a peak power density of 53 mW/cm2 at a peak current density of 115 mA/cm2. The polarization curve without OA (blue trace in Figure 4b) demonstrate a power density of only 8 mW/cm2 indicating the role of OA as an efficient electron acceptor in the proposed Zn battery. The galvanostatic polarization of Zn-OA battery at different current densities, Figure 4c, indicates a decrease in operating voltage when the rate is increased which is typical of a battery as mentioned earlier. The individual electrode polarizations, Figure 4d, suggests that the cathode limit the overall cell performance. The reduction of OA to glycolic acid is a multi-electron transfer reaction,58-60 which coupled with its limited solubility (0.7 M) could be responsible for this performance limitation. The volumetric discharge capacity (with respect to the volume of the catholyte) is close to 60 Ah/L (Figure S10, Supporting Information) which is again attributed to limited solubility, sluggish electrode kinetics and mass transport limitations of OA. Theoretical discharge capacity of Zn-OA battery is 850 mAh/g of oxalic acid, and the experimental capacity is close to 705 mAh/g (at 20 mA/cm2 in Figure


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4c). The lower discharge capacity with respect to theoretical discharge capacity could be due to electron and mass transport limitations at the cathode due to multi-electron characteristics of OA reduction to alcohols.58-60

(a)

(b)

(c)

(d)

Figure 4. (a) Single electrode potentials of Zn anode in 6 M KOH and Pb cathode in 2 M H2SO4 containing 0.7 M OA. (b) Polarization curves of Zn-organic reactor battery with and without OA. (c) Discharge curves of the Zn-OA battery at different current densities and (d) cathodic and anodic half-cell polarization curves. The product obtained from the battery is confirmed to be glycolic acid by colorimetric test with 2,7-dihydroxynaphthalene and UV-vis spectroscopy, Figure 5a. The formaldehyde formed by the reaction of glycolic acid with conc. H2SO4 at 100C reacts with 2,7-dihydroxynaphthalene


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to produce 2,2',7,7'-tetrahydroxy-1,1'-dinaphthylmethane. This compound on further oxidation yield a quinoidal compound (Scheme S2, Supporting Information) having a deep red-violet color with a characteristic absorption peak around 540 nm28,29 in the UV-visible spectroscopy, Figure 5a. This demonstrate the conversion of OA to alcohol in the cathode of the battery. The compound before discharge in battery resembled that of OA standard with its characteristic -OH stretching vibrations in the range 3250-3600 cm-1, and –C=O stretching vibrations in the range 1700-1780 cm-1, Figure 5b. In the discharge product obtained from the battery cathode, the FTIR spectra showed vibrational peaks in the range 2950-2850 cm-1, which are characteristics -CH functional group, Figure 5b. This indicates the conversion of OA to glycolic acid.

13

C NMR spectra (400

MHz, D2O) of standard OA demonstrate chemical shift at 161.71 (s, 2C) and standard glycolic acid demonstrate chemical shifts at δ 59.23 (s, C), and 176.22 (s, C), Figure 5c. The products from the battery cathode demonstrate chemical shifts at δ 59.16 (s, C) and 176.11 (s, C), suggesting the formation glycolic acid, Figure 5c. High resolution mass spectroscopy (HRMS) of the product obtained from the battery cathode, Figure 5d, demonstrate the presence of a dominant peak at 76.00 corresponding to parent ion of glycolic acid. All these confirm the conversion of oxalic acid to glycolic acid in the battery during the discharge chemistry. This suggests the reduction of OA to alcohols in the battery proceeds only till one of the –COOH functionality is reduced on the Pb electrode which may be due to the higher stability of formed glycolic acid compared to OA. Therefore, the reduction of 2nd –COOH in glycolic acid may require higher overpotentials than that required for 1st –COOH reduction. Based on these, the half-cell reactions are proposed (equations 9-10) for Zn-OA organic reactor battery and the complete cell reaction involves oxidation of Zn at the anode and the reduction of OA at the cathode yielding glycolic acid (equation 11).


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Anode: 𝑍𝑛2+ + 2ⅇ − → 𝑍𝑛 Cathode:

ESHE = -1.22 V (9)

𝐻𝑂𝑂𝐶 − 𝐶𝑂𝑂𝐻 + 4𝐻 + + 4ⅇ− → 𝐻𝑂𝑂𝐶 − 𝐶𝐻2 𝑂𝐻 + 𝐻2 𝑂

ESHE = -0.15 V (10)

Total cell reaction: 2𝑍𝑛 + 𝐻𝑂𝑂𝐶 − 𝐶𝑂𝑂𝐻 + 4𝐻 + → 2𝑍𝑛2+ + 𝐻2 0 + 𝐻𝑂𝑂𝐶 − 𝐶𝐻2 𝑂𝐻

Ecell = 1.07 V

(11)

The theoretical conversion efficiency for the conversion of OA to glycolic acid is estimated to be 73.5% (calculation S2, supporting information) based on 4 electron transfer reaction, and the incomplete conversion could be due to mass transport limitation and concentration polarization. The weight of obtained glycolic acid after battery discharge is 0.83 g (calculation S2, supporting information), therefore, the CE is close to 97% suggesting negligible parasitic chemistry at the battery cathode. The stability of Zn and Pb interfaces during long term polarization were investigated by SEM with EDS and XRD techniques (Figure S11, S12 and S13, supporting information). The behavior of Zn electrode was identical to Zn-NB organic reactor battery, SEM with EDS, Figure S11, Supporting Information, demonstrating oxidation and etching of Zn surface. The Pb cathode after galvanostatic polarization shows a significant change in surface roughness, SEM image, Figure S12, Supporting Information, which may be due to the oxidation of Pb surface in acidic medium, EDS pattern, Figure S12, Supporting Information. XRD pattern for used Pb remain unchanged even after long term polarization (Figure S13, Supporting Information), suggesting the oxide formation is restricted to the surface of the electrode. All these demonstrate that interfaces are reasonably stable and Zn-OA organic reactor battery is capable of generating an output power with simultaneous synthesis of fuel during the discharge chemistry.


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(a)

(b)

(c)

(d)

Page 20 of 32

Figure 5. (a) UV-vis spectra and colorimetric tests (inset) for the product obtained from the battery cathode along with OA and glycolic acid standards. The numbers (1), (2) and (3) stand for standard OA, discharge product from the battery cathode and standard glycolic acid respectively. (b) FTIR spectra and (c) 13C nuclear magnetic resonance (13C-NMR) spectroscopy (400 MHz) of standard OA, standard glycolic acid and the product obtained from the Zn-OA battery cathode during the discharge chemistry. (d) High Resolution Mass Spectrometry (HRMS) of the product obtained from the cathode of Zn-OA battery.


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In essence, we have demonstrated an unconventional battery chemistry which can generate an output power while the cathodic half-cell simultaneously functioning as an organic reactor. The battery demonstrated its potential to produce output power with concomitant generation of extremely useful chemicals such as aromatic amines and fuel such as alcohols during the discharge chemistry. Since aromatic amines are important precursors in many chemical and pharmaceutical industries and alcohols are safer energy carrier molecules, their production along with power generation in batteries open up new avenues in electro-organic synthesis and sustainable energy landscape.

ASSOCIATED CONTENT Supporting Information. The supporting information contains figures S1-S13, Tables S1, Scheme S1-S2 and Calculations S1-S2.

AUTHOR INFORMATION Corresponding Author * Email: [email protected]. Present Address Department of chemistry and centre for energy science, Indian Institute of Science Education and Research Pune, Dr. Homi Bhabha road, Pashan, Pune, India -411008. Author Contributions All authors have contributed to the manuscript. All authors have given approval to the final version of the manuscript. ‡ These authors contributed equally.


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ACKNOWLEDGMENT MOT acknowledges DST-SERB, MHRD and DST-Nanomission for financial assistance. Notes The authors declare no conflict of interest.

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Redox Couple. Energy and Environmental Science 2015, 8 (5), 1456–1462. DOI 10.1039/c5ee00192g.


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TABLE OF CONTENTS GRAPHIC

Electro-organic synthesis which satisfies majority of the postulates of green chemistry is demonstrated in a battery during electricity generation.


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Zinc Battery Driven by an Electro-Organic Reactor ... - ACS Publications

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