Direct Evidence for a Sequential Electron Transfer-Proton Transfer Mechanism in the PCET Reduction of a Metal Hydroxide Catalyst.

The proton-coupled electron transfer (PCET) mechanism for the reaction Mox-OH + e- + H+ → Mred-OH2 was determined through the kinetic resolution of the independent electron transfer (ET) and proton transfer (PT) steps. The reaction of interest was triggered by visible light excitation of [RuII(tpy)(bpy')H2O]2+, RuII-OH2, where tpy is 2,2':6',2″-terpyridine and bpy' is 4,4'-diaminopropylsilatrane-2,2'-bipyridine, anchored to In2O3:Sn (ITO) thin films in aqueous solutions. Interfacial kinetics for the PCET reduction reaction were quantified by nanosecond transient absorption spectroscopy as a function of solution pH and applied potential. Data acquired at pH = 5-10 revealed a stepwise electron transfer-proton transfer (ET-PT) mechanism, while kinetic measurements made below pKa(RuIII-OH/OH2) = 1.3 were used to study the analogous interfacial reaction, where electron transfer was the only mechanistic step. Analysis of this data with a recently reported multichannel kinetic model was used to construct a PCET zone diagram and supported the assignment of an ET-PT mechanism at pH = 5-10. Ultimately, this study represents a unique example among Mox-OH/Mred-OH2 reactivity where the protonation and oxidation states of the intermediate were kinetically and spectrally resolved to firmly establish the PCET mechanism.

General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System.

The pH dependence of proton-coupled electron transfer (PCET) reactions, which are critical to many chemical and biological processes, is a powerful probe for elucidating their fundamental mechanisms. Herein, a general, multichannel kinetic model is introduced to describe the pH dependence of both homogeneous and electrochemical PCET reactions. According to this model, a weak pH dependence can arise from the competition among multiple sequential and concerted PCET channels involving different forms of the redox species, such as protonated and deprotonated forms, as well as different proton donors and acceptors. The contribution of each channel is influenced by the relative populations of the reactant species, which often depend strongly on pH, leading to complex pH dependence of PCET apparent rate constants. This model is used to explain the origins of the experimentally observed weak pH dependence of the electrochemical PCET apparent rate constant for a ruthenium-based water oxidation catalyst attached to a tin-doped In2O3 (ITO) surface. The weak pH dependence is found to arise from the intrinsic differences in the rate constants of participating channels and the dependence of their relative contributions on pH. This model predicts that the apparent maximum rate constant will become pH-independent at higher pH, which is confirmed by experimental measurements. Our analysis also suggests that the dominant channels are electron transfer at lower pH and sequential PCET via electron transfer followed by fast proton transfer at higher pH. This work highlights the importance of considering multiple competing channels simultaneously for PCET processes.

Synthesis and Surface Attachment of Molecular Re(I) Complexes Supported by Functionalized Bipyridyl Ligands.

Eleven 2,2'-bipyridine (bpy) ligands functionalized with attachment groups for covalent immobilization on silicon surfaces were prepared. Five of the ligands feature silatrane functional groups for attachment to metal oxide coatings on the silicon surfaces, while six contain either alkene or alkyne functional groups for attachment to hydrogen-terminated silicon surfaces. The bpy ligands were coordinated to Re(CO)5Cl to form complexes of the type Re(bpy)(CO)3Cl, which are related to known catalysts for CO2 reduction. Six of the new complexes were characterized using X-ray crystallography. As proof of principle, four molecular Re complexes were immobilized on either a thin layer of TiO2 on silicon or hydrogen-terminated silicon. The surface-immobilized complexes were characterized using X-ray photoelectron spectroscopy, IR spectroscopy, and cyclic voltammetry (CV) in the dark and for one representative example in the light. The CO stretching frequencies of the attached complexes were similar to those of the pure molecular complexes, but the CVs were less analogous. For two of the complexes, comparison of the electrocatalytic CO2 reduction performance showed lower CO Faradaic efficiencies for the immobilized complexes than the same complex in solution under similar conditions. In particular, a complex containing a silatrane linked to bpy with an amide linker showed poor catalytic performance and control experiments suggest that amide linkers in conjugation with a redox-active ligand are not stable under highly reducing conditions and alkyl linkers are more stable. A conclusion of this work is that understanding the behavior of molecular Re catalysts attached to semiconducting silicon is more complicated than related complexes, which have previously been immobilized on metallic electrodes.

A New Class of Metal-Cyclam-Based Zirconium Metal-Organic Frameworks for CO2 Adsorption and Chemical Fixation.

Metal-organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO2 uptake capacity (up to ∼9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO2 with epoxides, including sterically hindered epoxides. The MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.

Surface Immobilization of a Re(I) Tricarbonyl Phenanthroline Complex to Si(111) through Sonochemical Hydrosilylation.

A sonochemical-based hydrosilylation method was employed to covalently attach a rhenium tricarbonyl phenanthroline complex to silicon(111). fac-Re(5-(p-Styrene)-phen)(CO)3Cl (5-(p-styrene)-phen = 5-(4-vinylphenyl)-1,10-phenanthroline) was reacted with hydrogen-terminated silicon(111) in an ultrasonic bath to generate a hybrid photoelectrode. Subsequent reaction with 1-hexene enabled functionalization of remaining atop Si sites. Attenuated total reflectance-Fourier transform infrared spectroscopy confirms attachment of the organometallic complex to silicon without degradation of the organometallic core, supporting hydrosilylation as a strategy for installing coordination complexes that retain their molecular integrity. Detection of Re(I) and nitrogen by X-ray photoelectron spectroscopy (XPS) further support immobilization of fac-Re(5-(p-styrene)-phen)(CO)3Cl. Cyclic voltammetry and electrochemical impedance spectroscopy under white light illumination indicate that fac-Re(5-(p-styrene)-phen)(CO)3Cl undergoes two electron reductions. Mott-Schottky analysis indicates that the flat band potential is 239 mV more positive for p-Si(111) co-functionalized with both fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene than when functionalized with 1-hexene alone. XPS, ultraviolet photoelectron spectroscopy, and Mott-Schottky analysis show that functionalization with fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene introduces a negative interfacial dipole, facilitating reductive photoelectrochemistry.

Nickel(II)-modified covalent-organic framework film for electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF).

Electrochemical oxidation of 5-hydroxymethylfurfural (HMF) is a promising synthetic route for 2,5-furandicarboxylic acid (FDCA) production. Here, we prepared a nickel(ii)-modified covalent-organic framework (COF) film TpBpy-Ni@FTO for HMF electrooxidation. With a high conversion of HMF (96%), TpBpy-Ni@FTO afforded a 58% FDCA yield. This work underlines the great potential of COF-based materials in electrocatalysis.

Study of Electrocatalytic Properties of Metal-Organic Framework PCN-223 for the Oxygen Reduction Reaction.

A highly robust metal-organic framework (MOF) constructed from Zr6 oxo clusters and Fe(III) porphyrin linkers, PCN-223-Fe was investigated as a heterogeneous catalyst for oxygen reduction reaction (ORR). Films of the framework were grown on a conductive FTO substrate and showed a high catalytic current upon application of cathodic potentials and achieved high H2O/H2O2 selectivity. In addition, the effect of the proton source on the catalytic performance was also investigated.

Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film.

Water oxidation, a key component in artificial photosynthesis, requires high overpotentials and exhibits slow reaction kinetics that necessitates the use of stable and efficient heterogeneous water-oxidation catalysts (WOCs). Here, we report the synthesis of UiO-67 metal-organic framework (MOF) thin films doped with [Ru(tpy)(dcbpy)OH2 ]2+ (tpy=2,2':6',2''-terpyridine, dcbpy=5,5'-dicarboxy-2,2'-bipyridine) on conducting surfaces and their propensity for electrochemical water oxidation. The electrocatalyst oxidized water with a turnover frequency (TOF) of (0.2±0.1) s-1 at 1.71 V versus the normal hydrogen electrode (NHE) in buffered solution (pH∼7) and exhibited structural and electrochemical stability. The electroactive sites were distributed throughout the MOF thin film on the basis of scan-ratedependent voltammetry studies. This work demonstrates a promising way to immobilize large concentrations of electroactive WOCs into a highly robust MOF scaffold and paves the way for future photoelectrochemical water-splitting systems.