Sodium-coupled electron transfer reactivity of metal-organic frameworks containing titanium clusters: the importance of cations in redox chemistry.

Stoichiometric reduction reactions of two metal-organic frameworks (MOFs) by the solution reagents (M = Cr, Co) are described. The two MOFs contain clusters with Ti8O8 rings: Ti8O8(OH)4(bdc)6; bdc = terephthalate (MIL-125) and Ti8O8(OH)4(bdc-NH2)6; bdc-NH2 = 2-aminoterephthalate (NH2-MIL-125). The stoichiometry of the redox reactions was probed using solution NMR methods. The extent of reduction is greatly enhanced by the presence of Na+, which is incorporated into the bulk of the material. The roughly 1 : 1 stoichiometry of electrons and cations indicates that the storage of e- in the MOF is tightly coupled to a cation within the architecture, for charge balance.

Cation Effects on the Reduction of Colloidal ZnO Nanocrystals.

The effects of a variety of monatomic cations (H+, Li+, Na+, K+, Mg2+, and Ca2+) and larger cations (decamethylcobaltocenium and tetrabutylammonium) on the reduction of colloidal ZnO nanocrystals (NCs) are described. Suspensions of "TOPO"-capped ZnO NCs in toluene/THF were treated with controlled amounts of one-electron reductants (CoCp*2 or sodium benzophenone anion radical) and cations. Equilibria were quickly established and the extent of NC reduction was quantified via observation of the characteristic near-IR absorbance of conduction band electrons. Addition of excess reductant with or without added cations led to a maximum average number of electrons per ZnO NC, which was dependent on the NC volume and on the nature of the cation. Electrons are transferred to the ZnO NCs in a stoichiometric way, roughly one electron per monovalent cation and roughly two electrons per divalent cation. This shows that cations are charge-balancing the added electrons in ZnO NCs. Overall, our experiments provide insight into the thermodynamics of charge storage and relate the colloidal chemistry of ZnO with bulk oxide semiconductors. They indicate that the apparent band energies of colloidal ZnO are highly dependent on cation/electrolyte composition and concentration, as is known for bulk interfaces, and that electrons and cations are added stoichiometrically to balance charge, similar to the behavior of Li+-batteries.

Proton-Controlled Reduction of ZnO Nanocrystals: Effects of Molecular Reductants, Cations, and Thermodynamic Limitations.

Charge carriers (electrons) were added to ZnO nanocrystals (NCs) using the molecular reductants CoCp*2 and CrCp*2 [Cp* = η(5)-pentamethylcyclopentadienyl]. The driving force for electron transfer from the reductant to the NCs was varied systematically by the addition of acid, which lowers the energy of the NC orbitals. In the presence of excess reductant, the number of electrons per NC (⟨ne(-)⟩) reaches a maximum, beyond which the addition of more acid has no effect. This ⟨ne(-)⟩max varies with the NC radius with an r(3) dependence, so the density of electrons (⟨Ne(-)⟩max) is constant over a range of NC sizes. ⟨Ne(-)⟩max = 4.4(1.0) × 10(20) cm(-3) for CoCp*2 and 1.3(0.5) × 10(20) cm(-3) for the weaker reducing agent, CrCp*2. Up until the saturation point, the addition of electrons is linear with respect to protons added. This linearity contrasts with the typical description of hydrogen atom-like states (S, P, etc.) in the conduction band. The 1:1 relationship of ⟨ne(-)⟩ with protons per NC and the dramatic dependence of ⟨Ne(-)⟩max on the nature of the cation (H(+) vs MCp*2(+)) suggest that the protons intercalate into the NCs under these conditions. The differences between the reductants, the volume dependence, calculations of the Fermi level using the redox couple, and a proposed model encompassing these effects are presented. This study illustrates the strong coupling between protons and electrons in ZnO NCs and shows that proton activity is a key parameter in nanomaterial energetics.

Low capping group surface density on zinc oxide nanocrystals.

The ligand shell of colloidal nanocrystals can dramatically affect their stability and reaction chemistry. We present a methodology to quantify the dodecylamine (DDA) capping shell of colloidal zinc oxide nanocrystals in a nonpolar solvent. Using NMR spectroscopy, three different binding regimes are observed: strongly bound, weakly associated, and free in solution. The surface density of bound DDA is constant over a range of nanocrystal sizes, and is low compared to both predictions of the number of surface cations and maximum coverages of self-assembled monolayers. The density of strongly bound DDA ligands on the as-prepared ZnO NCs is 25% of the most conservative estimate of the maximum surface DDA density. Thus, these NCs do not resemble the common picture of a densely capped surface ligand layer. Annealing the ZnO NCs in molten DDA for 12 h at 160 °C, which is thought to remove surface hydroxide groups, resulted in a decrease of the weakly associated DDA and an increase in the density of strongly bound DDA, to ca. 80% of the estimated density of a self-assembled monolayer on a flat ZnO surface. These findings suggest that as-prepared nanocrystal surfaces contain hydroxide groups (protons on the ZnO surfaces) that inhibit strong binding of DDA.

Effect of protons on the redox chemistry of colloidal zinc oxide nanocrystals.

Electron transfer (ET) reactions of colloidal 3-5 nm diameter ZnO nanocrystals (NCs) with molecular reagents are explored in aprotic solvents. Addition of an excess of the one-electron reductant Cp*2Co (Cp* = pentamethylcyclopentadienyl) gives NCs that are reduced by up to 1-3 electrons per NC. Protons can be added stoichiometrically to the NCs by either a photoreduction/oxidation sequence or by addition of acid. The added protons facilitate the reduction of the ZnO NCs. In the presence of acid, NC reduction by Cp*2Co can be increased to over 15 electrons per NC. The weaker reductant Cp*2Cr transfers electrons only to ZnO NCs in the presence of protons. Cp*2M(+) counterions are much less effective than protons at stabilizing reduced NCs. With excess Cp*2Co or Cp*2Cr, the extent of reduction increases roughly linearly with the number of protons added. Some of the challenges in understanding these results are discussed.

Catalytic hydrogen evolution from a covalently linked dicobaloxime.

A dicobaloxime in which monomeric Co(III) units are linked by an octamethylene bis(glyoxime) catalyzes the reduction of protons from p-toluenesulfonic acid as evidenced by electrocatalytic waves at -0.4 V vs. the saturated calomel electrode (SCE) in acetonitrile solutions. Rates of hydrogen evolution were determined from catalytic current peak heights (k(app) = 1100 ± 70 M(-1) s(-1)). Electrochemical experiments reveal no significant enhancement in the rate of H(2) evolution from that of a monomeric analogue: The experimental rate law is first order in catalyst and acid consistent with previous findings for similar mononuclear cobaloximes. Our work suggests that H(2) evolution likely occurs by protonation of reductively generated Co(II)H rather than homolysis of two Co(III)H units.

Titanium and zinc oxide nanoparticles are proton-coupled electron transfer agents.

Oxidation/reduction reactions at metal oxide surfaces are important to emerging solar energy conversion processes, photocatalysis, and geochemical transformations. Here we show that the usual description of these reactions as electron transfers is incomplete. Reduced TiO(2) and ZnO nanoparticles in solution can transfer an electron and a proton to phenoxyl and nitroxyl radicals, indicating that e(-) and H(+) are coupled in this interfacial reaction. These proton-coupled electron transfer (PCET) reactions are rapid and quantitative. The identification of metal oxide surfaces as PCET reagents has implications for the understanding and development of chemical energy technologies, which will rely on e(-)/H(+) coupling.