J. Gregory McAlpin

Electrochemical Water Oxidation with Cobalt-Based Electrocatalysts from pH 0–14: The Thermodynamic Basis for Catalyst Structure, Stability, and Activity

Building upon recent study of cobalt-oxide electrocatalysts in fluoride-buffered electrolyte at pH 3.4, we have undertaken a mechanistic investigation of cobalt-catalyzed water oxidation in aqueous buffering electrolytes from pH 0-14. This work includes electrokinetic studies, cyclic voltammetric analysis, and electron paramagnetic resonance (EPR) spectroscopic studies. The results illuminate a set of interrelated mechanisms for electrochemical water oxidation in alkaline, neutral, and acidic media with electrodeposited Co-oxide catalyst films (CoO(x)(cf)s) as well as for a homogeneous Co-catalyzed electrochemical water oxidation reaction. Analysis of the pH dependence of quasi-reversible features in cyclic voltammograms of the CoO(x)(cf)s provides the basis for a Pourbaix diagram that closely resembles a Pourbaix diagram derived from thermodynamic free energies of formation for a family of Co-based layered materials. Below pH 3, a shift from heterogeneous catalysis producing O(2) to homogeneous catalysis yielding H(2)O(2) is observed. Collectively, the results reported here provide a foundation for understanding the structure, stability, and catalytic activity of aqueous cobalt electrocatalysts for water oxidation.

EPR Evidence for Co(IV) Species Produced During Water Oxidation at Neutral pH

Thin-film water oxidation catalysts (Co-Pi) prepared by electrodeposition from phosphate electrolyte and Co(NO(3))(2) have been characterized by electron paramagnetic resonance (EPR) spectroscopy. Co-Pi catalyst films exhibit EPR signals corresponding to populations of both Co(II) and Co(IV). As the deposition voltage is increased into the region where water oxidation prevails, the population of Co(IV) rises and the population of Co(II) decreases. The changes in the redox speciation of the film can also be induced, in part, by prolonged water oxidation catalysis in the absence of additional catalyst deposition. These results provide spectroscopic evidence for the formation of Co(IV) species during water oxidation catalysis at neutral pH.

Electronic Structure Description of a [Co(III)3Co(IV)O4] Cluster: A Model for the Paramagnetic Intermediate in Cobalt-Catalyzed Water Oxidation

Multifrequency electron paramagnetic resonace (EPR) spectroscopy and electronic structure calculations were performed on [Co(4)O(4)(C(5)H(5)N)(4)(CH(3)CO(2))(4)](+) (1(+)), a cobalt tetramer with total electron spin S = 1/2 and formal cobalt oxidation states III, III, III, and IV. The cuboidal arrangement of its cobalt and oxygen atoms is similar to that of proposed structures for the molecular cobaltate clusters of the cobalt-phosphate (Co-Pi) water-oxidizing catalyst. The Davies electron-nuclear double resonance (ENDOR) spectrum is well-modeled using a single class of hyperfine-coupled (59)Co nuclei with a modestly strong interaction (principal elements of the hyperfine tensor are equal to [-20(±2), 77(±1), -5(±15)] MHz). Mims (1)H ENDOR spectra of 1(+) with selectively deuterated pyridine ligands confirm that the amount of unpaired spin on the cobalt-bonding partner is significantly reduced from unity. Multifrequency (14)N ESEEM spectra (acquired at 9.5 and 34.0 GHz) indicate that four nearly equivalent nitrogen nuclei are coupled to the electron spin. Cumulatively, our EPR spectroscopic findings indicate that the unpaired spin is delocalized almost equally across the eight core atoms, a finding corroborated by results from DFT calculations. Each octahedrally coordinated cobalt ion is forced into a low-spin electron configuration by the anionic oxo and carboxylato ligands, and a fractional electron hole is localized on each metal center in a Co 3d(xz,yz)-based molecular orbital for this essentially [Co(+3.125)(4)O(4)] system. Comparing the EPR spectrum of 1(+) with that of the catalyst film allows us to draw conclusions about the electronic structure of this water-oxidation catalyst.

Metal–Oxygen Isopolyhedra Assembled into Fullerene Topologies

Carbon-based fullerenes have received considerable attention since their discovery and are currently being produced on an industrial scale. Fullerenes are cage structures composed of 12 pentagons and several hexagons. Many fullerene topologies are possible, but selection criteria favor a small subset. C60 is the classic and most stable fullerene. [1] No smaller fullerene can be built without its topology containing adjacent pentagons, which destabilize the structure through increased curvature. For fullerenes with less than 60 C atoms, it is thought that those with the fewest adjacent pentagons will be the most stable because they minimize strain. 5] Fullerenes with less than 60 C atoms exist, for example C50, which can be stabilized as C50Cl10 by addition of Cl ligands. This structure does follow the minimal pentagon adjacency rule, but theoretical calculations suggest that pure C50 will not because sphericity is substantially increased when the number of adjacent pentagons is increased to six, as compared to five in the case of C50Cl10. [7] There is also considerable interest in inorganic fullerenelike materials; particular emphasis is on compounds such as MoS2 that tend to form onion-skin-like structures with useful materials properties. Molybdenum–oxygen heteropolyhedra have previously been found to form clusters with fullerene topologies, termed keplerates. Our earlier discovery of spherical clusters of uranyl peroxide polyhedra containing 24, 28, or 32 hexagonal bipyramids suggests that large clusters of metal–oxygen isopolyhedra with fullerene topologies may be synthesized. Of the three uranyl peroxide clusters described earlier, the 28-metal-ion cluster U28 has a fullerene topology with 12 pentagons and 4 hexagons, whereas the other two also contain squares in their topologies. We propose that assembly of metal–oxygen isopolyhedra into nanoscale fullerene topologies may be facilitated by judicious selection of structural building units. The rules that govern the formation of metal–oxygen cages are of interest, as such materials could have a variety of applications, including catalysis and synthesis of advanced materials. Assembly of metal–oxygen isopolyhedra into conventional fullerene topologies can only occur if at least the following conditions are met: 1) Each polyhedron must link to exactly three other polyhedra, and the most stable structures will occur when the connections between the metal–oxygen polyhedra are by the sharing of polyhedral edges. 2) The polyhedra must be geometrically compatible with forming topological pentagons and hexagons. 3) The three linkages emanating from any given polyhedron should be approximately coplanar to facilitate the cage geometry. 4) Linkages between polyhedra should be consistent with the bond-valence requirements of the shared polyhedral elements within the cage.

Rates of water exchange for two cobalt(II) heteropolyoxotungstate compounds in aqueous solution.

Polyoxometalate ions are used as ligands in water-oxidation processes related to solar energy production. An important step in these reactions is the association and dissociation of water from the catalytic sites, the rates of which are unknown. Here we report the exchange rates of water ligated to Co(II) atoms in two polyoxotungstate sandwich molecules using the (17)O-NMR-based Swift-Connick method. The compounds were the [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) and the larger αββα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-) ions, each with two water molecules bound trans to one another in a Co(II) sandwich between the tungstate ligands. The clusters, in both solid and solution state, were characterized by a range of methods, including NMR, EPR, FT-IR, UV-Vis, and EXAFS spectroscopy, ESI-MS, single-crystal X-ray crystallography, and potentiometry. For [Co(4)(H(2)O)(2)(B-α-PW(9)O(34))(2)](10-) at pH 5.4, we estimate: k(298)=1.5(5)±0.3×10(6) s(-1), ΔH(≠)=39.8±0.4 kJ mol(-1), ΔS(≠)=+7.1±1.2 J mol(-1) K(-1) and ΔV(≠)=5.6 ±1.6 cm(3) mol(-1). For the Wells-Dawson sandwich cluster (αββα-[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-)) at pH 5.54, we find: k(298)=1.6(2)±0.3×10(6) s(-1), ΔH(≠)=27.6±0.4 kJ mol(-1) ΔS(≠)=-33±1.3 J mol(-1) K(-1) and ΔV(≠)=2.2±1.4 cm(3) mol(-1) at pH 5.2. The molecules are clearly stable and monospecific in slightly acidic solutions, but dissociate in strongly acidic solutions. This dissociation is detectable by EPR spectroscopy as S=3/2 Co(II) species (such as the [Co(H(2)O)(6)](2+) monomer ion) and by the significant reduction of the Co-Co vector in the XAS spectra.

A 31P NMR Investigation of the CoPi Water‐Oxidation Catalyst

Beneath the sheets: (31) P NMR data suggests that phosphates are liberated freely in the interlayer of a cobalt-hydroxide water-oxidation catalyst. The cobalt-hydroxide sheets are separated by an interlayer region with water, counterions and phosphate, which help to shuttle protons as the layer develops charge.