Correlations between the Electronic Structure and Energetics of the Catalytic Steps in Homogeneous Water Oxidation Catalysis.

The development of an efficient electrocatalyst for the water oxidation reaction is limited by unfavorable scaling relations between catalytic intermediates, resulting in an overpotential. In contrast to heterogeneous catalysts, the electronic structure of homogeneous catalysts can be modified to a great extent due to a tailored ligand design. However, studies utilizing the tunability of organic ligands have rarely been conducted in a systematic manner and, as of yet, have not produced catalytic paths that avoid the aforementioned unfavorable scaling relations. To investigate the influence of electron-donating groups (EDGs) or electron-withdrawing groups (EWGs) on elementary steps in electrochemical water oxidation catalysis, cis-[Ru(bpy)2(H2O)]2+ (bpy = 2,2'-bipyridine) was selected as the scaffold that was modified with methyl, methoxy, chloro, and trifluoromethyl groups. This catalyst can undergo several electron transfer (ET), proton transfer (PT), and proton-coupled electron transfer (PCET) steps that were all probed experimentally. In this systematic study, it was found that PCET steps are relatively insensitive with respect to the presence of EDGs or EWGs, while the decoupled ET and PT steps are more heavily affected. However, the influence of the substituents decreases with an increasing oxidation state of Ru due to a lack of d-electrons available at the Ru center for π-backbonding to the bipyridine ligand. Therefore, the RuV/VI redox couple appears to be relatively unaffected by the substituent. Nevertheless, the implementation of EWGs can shift all oxidation events to a very narrow potential window. Not only do our findings illustrate how electronic substituents affect the entire potential energy landscape of the catalytic water oxidation reaction, but they also show that the cis-[Ru(bpy)2(H2O)]2+ compounds follow different design rules and scaling relations, as has been reported for every other oxygen evolution catalyst thus far.

Challenges in Elucidating the Free Energy Scheme of the Laccase Catalyzed Reduction of Oxygen.

Artificial redox catalysts are typically limited by unfavorable scaling relations of reaction intermediates leading to a significant overpotential in multi-electron redox reactions such as for example the oxygen reduction reaction (ORR). The multicopper oxidase laccase is able to catalyze the ORR in nature. In particular the high-potential variants show a remarkably low overpotential for the ORR and apparently do not suffer from such unfavorable scaling relations. Although laccases are intensively studied, it is presently unknown why the overpotential for ORR is so low and a clear description regarding the thermodynamics of the catalytic cycle and the underlying design principles is lacking. In order to understand the laccase catalyzed ORR from an electrochemical perspective, elucidation of the free energy scheme would be of high value. This article reviews the energetics of the proposed laccase catalyzed ORR mechanisms based on experimental and computational studies. However, there are still remaining challenges to overcome to elucidate the free energy scheme of laccase. Obtaining thermodynamic data on intermediates is hard or even impossible with analytical techniques. On the other hand, several computational studies have been performed with significantly different parameters and conditions, thus making a direct comparison difficult. For these reasons, a consensus on a clear free energy scheme is still lacking. We anticipate that ultimately conquering these challenges will result in a better understanding of laccase catalyzed ORR and will allow for the design of low overpotential redox catalysts.

Unusual Water Oxidation Mechanism via a Redox-Active Copper Polypyridyl Complex.

To improve Cu-based water oxidation (WO) catalysts, a proper mechanistic understanding of these systems is required. In contrast to other metals, high-oxidation-state metal-oxo species are unlikely intermediates in Cu-catalyzed WO because π donation from the oxo ligand to the Cu center is difficult due to the high number of d electrons of CuII and CuIII. As a consequence, an alternative WO mechanism must take place instead of the typical water nucleophilic attack and the inter- or intramolecular radical-oxo coupling pathways, which were previously proposed for Ru-based catalysts. [CuII(HL)(OTf)2] [HL = Hbbpya = N,N-bis(2,2'-bipyrid-6-yl)amine)] was investigated as a WO catalyst bearing the redox-active HL ligand. The Cu catalyst was found to be active as a WO catalyst at pH 11.5, at which the deprotonated complex [CuII(L-)(H2O)]+ is the predominant species in solution. The overall WO mechanism was found to be initiated by two proton-coupled electron-transfer steps. Kinetically, a first-order dependence in the catalyst, a zeroth-order dependence in the phosphate buffer, a kinetic isotope effect of 1.0, a ΔH⧧ value of 4.49 kcal·mol-1, a ΔS⧧ value of -42.6 cal·mol-1·K-1, and a ΔG⧧ value of 17.2 kcal·mol-1 were found. A computational study supported the formation of a Cu-oxyl intermediate, [CuII(L•)(O•)(H2O)]+. From this intermediate onward, formation of the O-O bond proceeds via a single-electron transfer from an approaching hydroxide ion to the ligand. Throughout the mechanism, the CuII center is proposed to be redox-inactive.

Elucidation of the Structure of a Thiol Functionalized Cu-tmpa Complex Anchored to Gold via a Self-Assembled Monolayer.

The structure of the copper complex of the 6-((1-butanethiol)oxy)-tris(2-pyridylmethyl)amine ligand (Cu-tmpa-O(CH2)4SH) anchored to a gold surface has been investigated. To enable covalent attachment of the complex to the gold surface, a heteromolecular self-assembled monolayer (SAM) of butanethiol and a thiol-substituted tmpa ligand was used. Subsequent formation of the immobilized copper complex by cyclic voltammetry in the presence of Cu(OTf)2 resulted in the formation of the anchored Cu-tmpa-O(CH2)4SH system which, according to scanning electron microscopy and X-ray diffraction, did not contain any accumulated copper nanoparticles or crystalline copper material. Electrochemical investigation of the heterogenized system barely showed any redox activity and lacked the typical CuII/I redox couple in contrast to the homogeneous complex in solution. The difference between the heterogenized system and the homogeneous complex was confirmed by X-ray photoelectron spectroscopy; the XPS spectrum did not show any satellite features of a CuII species but instead showed the presence of a CuI ion in a ∼2:3 ratio to nitrogen and a ∼2:7 ratio to sulfur. The +I oxidation state of the copper species was confirmed by the edge position in the X-ray absorption near-edge structure (XANES) region of the X-ray absorption spectrum. These results show that upon immobilization of Cu-tmpa-O(CH2)4SH, the resulting structure is not identical to the homogeneous CuII-tmpa complex. Upon anchoring, a novel CuI species is formed instead. This illustrates the importance of a thorough characterization of heterogenized molecular systems before drawing any conclusions regarding the structure-function relationships.