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Interrogation of electrocatalytic water oxidation mediated by a cobalt complexw

Derek J. Wasylenko,a Ryan D. Palmer,a Eduardo Schottb and Curtis P. Berlinguette*a
Downloaded by Ewha Womens University on 27 March 2013 Published on 13 January 2012 on http://pubs.rsc.org | doi:10.1039/C2CC16674G

Received 27th October 2011, Accepted 19th December 2011 DOI: 10.1039/c2cc16674g Examination of the aqueous electrochemistry of a Co(II) complex bearing a pentadentate ligand suggests that the catalytic current corresponding to water oxidation is molecular in origin, and does not emanate exclusively from Co-oxide phases formed in situ. We recently disclosed the electrochemical behaviour of a Co(II) complex, [Co(PY5)(OH2)](ClO4)2 (1; PY5 = 6-(bis(bis-2-pyridyl)methoxymethane)pyridine; Fig. 1) in aqueous media.1 Cyclic voltammograms (CVs) recorded at various pH levels demonstrated that the [CoIIOH2]2+ fragment of 1 undergoes a proton-coupled electron-transfer (PCET) step to furnish [CoIIIOH]2+, which is to our knowledge the rst example of a [MIIIOH]2+/[MIIOH2]2+ redox couple where M is a 3d transition metal.25 Another notable feature that emerged from this study was the identication of a second process at ca. 1.45 V (at pH 9.2; all potentials herein reported vs NHE) during the oxidative scan (Fig. 2 and Fig. S1, ESIw). We postulated that this process was indicative of a catalytic wave corresponding to water oxidation (eqn (1)). (Note that single-site, synthetic water oxidation catalysts containing 3d transition metals are rare.68) We put forward the proposal that this reactivity occurred upon formation of a [CoIVOH]3+ species that is reactive towards OH (see Fig. S2, ESIw),9 and that this reactive

Fig. 2 CVs recorded on a solution of [Co(OH2)6](ClO4)2 (red line; [Co] = 10 mM) and a solution of 1 (black line; [1] = 0.5 mM) at pH 9.2. The arrow indicates that the trend in the catalytic current (icat) diminishes with each sweep for both 1 and free Co(II).

metal species was made accessible by the stabilization of the metal ion within the pentadentate ligand framework of PY5.1012 Cognizant of the high catalytic activity of Co-oxide solids, we had carried out numerous control experiments to rule out the possibility that the complex was degrading into a catalytically active amorphous Co-oxide lm (a-CoOx).1316 We report herein, however, an independent set of control experiments that revealed that very low concentrations of free Co(II) (i.e., [Co(OH2)6](ClO4)2) give rise to a catalytic response that is closely related to that of 1 (Fig. 2). This observation, along with a recent evaluation of another Co-containing homogeneous water oxidation catalyst (WOC),17,18 prompted us to scrutinize the catalytic behaviour of 1 in greater detail. Despite the similar behaviour of 1 and [Co(OH2)6]2+, we show herein data that lends credibility to the catalytic activity of 1 being molecular in nature, and not exclusively to the formation of a catalytically active Co-oxide solid that forms from adventitious Co(II). 2 OH - O2 + 2 H+ + 4 e Eo = 1.229 V 0.059 (pH) (1)

Fig. 1 Molecular representation of [CoII(PY5)(OH2)](ClO4)2 (1).1 The counteranion and H atoms of PY510,11 are omitted for clarity.
a

Department of Chemistry, University of Calgary and the Institute for Sustainable Energy, Environment & Economy, University of Calgary, 2500 University Drive N.W., Calgary, Canada T2N-1N4. E-mail: cberling@ucalgary.ca; Tel: +1-403-220-3856 b Departamento de Ciencias Quimicas, Universidad Andres Bello, Republica 275, Santiago, Chile w Electronic supplementary information (ESI) available: Synthesis and characterization details, and kinetic, DFT and crystallographic data. See DOI: 10.1039/c2cc16674g

Our inspiration for studying the catalytic water oxidation activity of 1 was drawn from a combination of the prevalence of heterogeneous Co-based WOCs in the literature,1316 and our stability studies of homogenous Ru-based WOCs.19,20 Because we determined that it is the bond trans to the oxo ligand of single-site Ru WOCs that is rst compromised during catalysis,19,20 we converged on 1 with the view that PY5 would retain this particular bond to render a suciently robust WOC. The stability engendered by the ligand was conrmed by the observation of the unprecedented PCET
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step, [CoIIIOH]2+/[CoIIOH2]2+.1 While our electrochemical studies of Co complexes bearing ligands of lower denticity displayed a clear propensity to form a-CoOx upon an oxidative sweep in aqueous media,21 1 did not lead to lm deposition over a pH range of 7.610.3. We therefore attributed the increase in current at ca. 1.4 V to water oxidation catalyzed by 1.1 While we did document the formation of a-CoOx on the electrode at pH > 10.3, we ruled out the deposition of a-CoOx under less basic conditions based on homogeneity tests (Fig. S3, ESIw), and a catalytic response that was notably dierent than that of a-CoOx;1316 e.g., the catalytic current (icat) in the CV of 1 was pH-independent and oset, it lacked the so-called prefeature (i.e., a small rise in current prior to catalysis), and subsequent scans did not display a rise in icat to indicate lm deposition (Fig. 2). Condent that we had dismissed the deposition of a-CoOx, a recent examination by Stracke and Finke brought to our attention a catalytic response at remarkably low concentrations of Co(II).17 This observation prompted us to revisit a similar set of control experiments, and we were able to subsequently conrm the ndings; i.e., CVs of dilute [Co(OH2)6]2+ solutions displayed a catalytic wave at >1.4 V over the pH range 712 (Fig. S4, ESIw). Moreover, the value of icat diminished with subsequent scans (Fig. 2) and did not coincide with the formation of a deposited lm (Fig. S5, ESIw). On this basis, we support the notion17 that catalytically active Co-oxide NPs form in solution at low Co(II) concentrations.22,23 Of relevance to this study is the fact that the catalytic behaviour of these dilute [Co(OH2)6]2+ solutions is strikingly similar to the catalytic wave that emerges during the oxidative scans of 1 (Fig. 2). We therefore set out to resolve whether 1 is indeed an authentic WOCa task made dicult by the need for only 10 mM of adventitious Co(II) in solution to match the catalytic response of 1; i.e., an impurity level of merely ca. 12% free Co(II). This amount of impurity in the bulk sample, however, is not supported by the elemental analysis of 1 (calculated (%) for C29H27Cl2N5O11Co: C 46.36, H 3.62, N 9.32; found: C 46.24, H 3.68, N 9.24). Moreover, an exhaustive examination of 1 from independent preparations under various reaction conditions is reproducible, thereby casting doubt on free Co(II) being carried forward from synthetic preparations. We then considered free Co(II) being leached from the ligand in situ, which has been shown to be possible for other catalysts.17 The robust ligand pocket was conrmed by monitoring the stability of 1 spectrophotometrically to show that the complex is stable at pH 7 and 10.98 for at least 3 h (Fig. S6, ESIw). The temporal stability of the complex was also veried by seeing no changes in the ratio of icat to the diusional current (id) of the Co(III)/Co(II) couple after cycling over the 01.6 V potential range several times over a 3 h time period (Fig. S7, ESIw). Moreover, the catalytic response of 1 and [Co(OH2)6]2+ at various pH levels are not entirely congruent (Fig. 3). In the case of 1, for example, a progressively higher icat is measured at increasing pH levels (Fig. 3a), while the same set of experiments on solutions of [Co(OH2)6]2+ do not show the same trend at various pH levels (Fig. 3b). These data provide evidence that distinctively dierent catalytic species exist in each of the experiments and suggest that at least part of the measured electrocatalytic current is molecular in origin and does not arise from a decomposition product.
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Downloaded by Ewha Womens University on 27 March 2013 Published on 13 January 2012 on http://pubs.rsc.org | doi:10.1039/C2CC16674G

Fig. 3 Cyclic voltammograms recorded on a (a) 0.5 mM solution of 1 and (b) 10 mM solution of [Co(OH2)6](ClO4)2 highlighting the disparate catalytic activity at various pH levels. (The pH of the 0.1 M KPi solution was adjusted using either 5 M KOH or HNO3. Scan rate = 20 mV s1; working electrode = 3 mm glassy carbon; counter electrode = Pt; reference electrode = Cu/CuSO4).

The electrochemical behaviour of 1 and [Co(OH2)6]2+ was also measured in (Bu4N)(BF4)/propylene carbonate (PC) solutions to examine how an aprotic environment aects the oxidative behavior (Fig. S8, ESIw). While a distinct Co(III)/ Co(II) redox couple for 1 was observed at 0.78 V, a second oxidation wave was not observed up to ca. 2 V in the absence of water. This observation supports the notion that a redox leveling PCET step is needed to access the high-valent catalytically active species.1 When water and KOH were added to the mixture, the Co(III)/Co(II) redox couple was cathodically shifted by ca. 0.6 V; a second closely spaced oxidative wave was also observed that we ascribe to the coordination of PC.24 An oxidative sweep reveals a peak at Ep,a E 1.0 V, which we tentatively assign as the formation of [CoIVOH]3+,25 followed by a signal of lower intensity at B1.5 V. An oxidative scan of [Co(OH2)6]2+ under the same conditions reveals a shoulder at 1.0 V that precedes an intense signal centred at B1.5 V. This dissimilar electrochemical behaviour between 1 and Co(II) over the 1.01.8 V range suggests that the catalytic response of 1 has a contribution from the molecular species; however, we cannot unambiguously rule out some contribution to icat from Co-oxide NPs that form in situ. While the catalytic behaviour of 1 does share traits consistent with a Co-oxide solid that can form at low concentrations of Co(II), our collective observations suggest that 1 is indeed a WOC.1 We therefore carried out a more extensive analysis of 1 to gain mechanistic insight into the catalytic process. For example, the background-corrected peak current of the catalytic wave (icat) for 1, which is proportional to the maximum rate of the reaction (and analogous to initial rates), led to the determination of the rate law expressed in eqn (2) (where kcat and kobs are the respective catalytic and observed reaction rate coecients). The reaction was determined to be rst-order in [1] based on the linear dependence of icat as a function of [1] (Fig. S9, ESIw), and the corresponding plot of log(icat) vs log([1]) that renders a slope of ca. 1 (Fig. S10, ESIw). The reaction was determined to be rst-order in [OH] given that a plot of log(i2 cat) vs pH produces a slope of 1 [eqn (2) and (3); Fig. S10, ESIw]. rate = kcat[1][OH] = kobs[1] icat = ncatFA[1]o(kobsD1)
1/2

(2) (3)

These results suggest that the rate-limiting event involves a single Co site. The overall reaction rate law is aligned with a RDS involving attack of the high-valent [CoIVOH]3+
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fragment by OH. Lending credence to this claim are the observations that: (i) icat is diminished at progressively higher scan rates, which is consistent with a rate-limiting chemical process (such as dioxygen bond formation) prior to electrontransfer;24,26 and (ii) a H/D kinetic isotope eect (KIE) of 4.7 (Fig. S11, ESIw) that is consonant with a RDS involving proton-transfer. We considered the alternative possibility that OH abstracts a proton from [CoIVOH]3+ prior to dioxygen formation; however, the high basicity of the resultant oxo ligand would not likely react quickly with H2O or OH to form an OO bond. DFT calculations oer further support for these proposed catalytic intermediates (Fig. S12 and S13, ESIw). The kobs values were also quantied for 1 (see the caption for Fig. S14 (ESIw) for details),26,27 but the lingering possibility that Co-oxide NPs exist in solution render this analysis potentially meaningless. A similar kinetic analysis was carried out on dilute solutions of [Co(OH2)6]2+ to reveal a trend in the scan-rate dependent behaviour similar to that of 1 (Fig. S15, ESIw); however, there remain some notable dierences (e.g., note disparities in Fig. S14c and S15c, ESIw) that do not clearly resolve the homogeneity issue at hand. Moreover, a KIE value of 10.8 was measured for [Co(OH2)6]2+ (Fig. S16, ESIw), which is much larger than that measured for 1. We conclude that 1 is indeed a WOC; however, it remains dicult for us to conclusively rule out that NPs formed in solution near the electrode make a contribution to the catalytic current. These results draw attention to the potential perils involved in characterizing homogeneous WOCs,17,2831 and the challenge in separating the catalytic activity of molecular fragments from that of metal-oxide solids that may co-exist in solution. This work was supported by Alberta Ingenuity, Canada Research Chairs, Canada Foundation for Innovation and NSERC. We would also like to thank Ramiro Arratia-Perez (Universidad Andres Bello) for assistance with DFT calculations.

Notes and references

1 D. J. Wasylenko, C. Ganesamoorthy, J. Borau-Garcia and C. P. Berlinguette, Chem. Commun., 2011, 47, 42514253. 2 C. Costentin, M. Robert, J.-M. Saveant and A.-L. Teillout, Proc. Natl. Acad. Sci. U. S. A., 2009, 106, 1182911836. 3 M. H. V. Huynh and T. J. Meyer, Chem. Rev., 2007, 107, 50045064. 4 J. J. Warren, T. A. Tronic and J. M. Mayer, Chem. Rev., 2010, 110, 69617001. 5 This statement applies to complexes containing a single metal site. Note that PCET has been documented in a dimeric Mn complex: C. W. Cady, K. E. Shinopoulos, R. H. Crabtree and G. W. Brudvig, Dalton Trans., 2010, 39, 39853989. 6 D. K. Dogutan, R. McGuire and D. G. Nocera, J. Am. Chem. Soc., 2011, 133, 91789180.

7 W. C. Ellis, N. D. McDaniel, S. Bernhard and T. J. Collins, J. Am. Chem. Soc., 2010, 132, 1099010991. ` , I. Garcia-Bosch, L. Go mez, J. J. Pla and 8 J. L. Fillol, Z. Codola M. Costas, Nat. Chem, 2011, 3, 807813. 9 Water oxidation was conrmed by the detection of dioxygen in the headspace of the reaction ask. Control experiments on the free ligand and [Zn(PY5)(OH2)](ClO4)2 also ruled out the catalytic wave being formed as a consequence of ligand degradation. 10 R. T. Jonas and T. D. P. Stack, J. Am. Chem. Soc., 1997, 119, 85668567. 11 M. E. de Vries, R. M. La Crois, G. Roelfes, H. Kooijman, A. L. Spek, R. Hage and B. L. Feringa, Chem. Commun., 1997, 15491550. 12 A similar ligand scaold about a Co ion has been shown to reduce water: Y. Sun, J. P. Bigi, N. A. Piro, M. L. Tang, J. R. Long and C. J. Chang, J. Am. Chem. Soc., 2011, 133, 92129215. 13 Y. Surendranath, M. W. Kanan and D. G. Nocera, J. Am. Chem. Soc., 2010, 132, 1650116509. 14 M. W. Kanan, J. Yano, Y. Surendranath, M. Dinca, V. K. Yachandra and D. G. Nocera, J. Am. Chem. Soc., 2010, 132, 1369213701. 15 M. W. Kanan and D. G. Nocera, Science, 2008, 321, 10721075. 16 J. B. Gerken, J. G. McAlpin, J. Y. C. Chen, M. L. Rigsby, W. H. Casey, R. D. Britt and S. S. Stahl, J. Am. Chem. Soc., 2011, 133, 1443114442. 17 J. J. Stracke and R. G. Finke, J. Am. Chem. Soc., 2011, 133, 1487214875. 18 Q. Yin, J. M. Tan, C. Besson, Y. V. Geletii, D. G. Musaev, A. E. Kuznetsov, Z. Luo, K. I. Hardcastle and C. L. Hill, Science, 2010, 328, 342345. 19 D. J. Wasylenko, M. A. Henderson, C. Ganesamoorthy, B. D. Koivisto, H. G. Ostho and C. P. Berlinguette, J. Am. Chem. Soc., 2010, 132, 1609416106. 20 D. J. Wasylenko, C. Ganesamoorthy, B. D. Koivisto, M. A. Henderson and C. P. Berlinguette, Inorg. Chem., 2010, 49, 22022209. 21 Unpublished results. 22 Colloids were not detected by dynamic light-scattering methods, presumably due to the low metal concentrations used in this study. While we cannot fully exclude the possibility of higher-nuclearity molecular species being responsible for dioxygen evolution (e.g., ref. 23), this scenario is not elaborated herein because the kinetic behavior is aligned with NP formation. 23 M. Anbar and I. Pecht, J. Am. Chem. Soc., 1967, 89, 2553. 24 Z. Chen, J. J. Concepcion, H. Luo, J. F. Hull, A. Paul and T. J. Meyer, J. Am. Chem. Soc., 2010, 132, 1767017673. 25 Spectroscopic studies are underway to conrm the Co(IV) species. 26 P. Zanello, Inorganic Electrochemistry: Theory, Practice and Application, The Royal Society for Chemistry, Cambridge, UK, 2003. 27 A. J. Bard and L. R. Faulkner, Electrochemical Methods. Fundamentals and Applications, John Wiley & Sons, New York, 2nd edn, 2001. 28 N. D. Schley, J. D. Blakemore, N. K. Subbaiyan, C. D. Incarvito, F. DSouza, R. H. Crabtree and G. W. Brudvig, J. Am. Chem. Soc., 2011, 133, 10473. 29 J. D. Blakemore, N. D. Schley, G. W. Olack, C. D. Incarvito, G. W. Brudvig and R. H. Crabtree, Chem. Sci., 2011, 2, 9498. 30 R. K. Hocking, R. Brimblecombe, L. Y. Chang, A. Singh, M. H. Cheah, C. Glover, W. H. Casey and L. Spiccia, Nat. Chem., 2011, 3, 461. 31 R. H. Crabtree, Chem. Rev., 2011, DOI: 10.1021/cr2002905.

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