Single-Atom Cobalt Catalysts Coupled with Peroxidase Biocatalysis for C-H Bond Oxidation.

This paper reports a robust strategy to catalyze in situ C-H oxidation by combining cobalt (Co) single-atom catalysts (SACs) and horseradish peroxidase (HRP). Co SACs were synthesized using the complex of Co phthalocyanine with 3-propanol pyridine at the two axial positions as the Co source to tune the coordination environment of Co by the stepwise removal of axial pyridine moieties under thermal annealing. These structural features of Co sites, as confirmed by infrared and X-ray absorption spectroscopy, were strongly correlated to their reactivity. All Co catalysts synthesized below 300 °C were inactive due to the full coordination of Co sites in octahedral geometry. Increasing the calcination temperature led to an improvement in catalytic activity for reducing O2, although molecular Co species with square planar coordination obtained below 600 °C were less selective to reduce O2 to H2O2 through the two-electron pathway. Co SACs obtained at 800 °C showed superior activity in producing H2O2 with a selectivity of 82-85% in a broad potential range. In situ production of H2O2 was further coupled with HRP to drive the selective C-H bond oxidation in 2-naphthol. Our strategy provides new insights into the design of highly effective, stable SACs for selective C-H bond activation when coupled with natural enzymes.

Well-defined surface catalytic sites for solar CO2 reduction: heterogenized molecular catalysts and single atom catalysts.

Exciting progress has been made in the area of solar fuel generation by CO2 reduction. New photocatalytic materials containing well-defined surface catalytic sites have emerged in recent years, including heterogenized molecular catalysts and single atom catalysts. This Feature Article summarizes our recent research in this area, together with brief discussions of relevant literature. In our effort to obtain heterogenized molecular catalysts, a diimine-tricarbonyl Re(I) complex and a tetraaza macrocyclic Co(III) compound were covalently attached to different surfaces, and the effects of ligand derivatization and surface characteristics on their structures and photocatalytic activities were investigated. Single atom catalysts combine the advantages of homogeneous and heterogeneous catalysis. A single-site cobalt catalyst was prepared on graphitic carbon nitride, which demonstrated excellent activity in selective CO2 reduction under visible-light irradiation. Doping carbon nitride with carbon was found to have profound effects on the structure and activity of the single-site cobalt catalyst. Our research achievements are presented to emphasize how spectroscopic techniques, including infrared, UV-visible, electron paramagnetic resonance, and X-ray absorption spectroscopies, could be combined with catalyst synthesis and computation modeling to understand the structures and properties of well-defined surface catalytic sites at the molecular level. This article also highlights challenges and opportunities in the broad context of solar CO2 reduction.

Probing active sites for carbon oxides hydrogenation on Cu/TiO2 using infrared spectroscopy.

The valorization of carbon oxides on metal/metal oxide catalysts has been extensively investigated because of its ecological and economical relevance. However, the ambiguity surrounding the active sites in such catalysts hampers their rational development. Here, in situ infrared spectroscopy in combination with isotope labeling revealed that CO molecules adsorbed on Ti3+ and Cu+ interfacial sites in Cu/TiO2 gave two disparate carbonyl peaks. Monitoring each of these peaks under various conditions enabled tracking the adsorption of CO, CO2, H2, and H2O molecules on the surface. At room temperature, CO was initially adsorbed on the oxygen vacancies to produce a high frequency CO peak, Ti3+-CO. Competitive adsorption of water molecules on the oxygen vacancies eventually promoted CO migration to copper sites to produce a low-frequency CO peak. In comparison, the presence of gaseous CO2 inhibits such migration by competitive adsorption on the copper sites. At temperatures necessary to drive CO2 and CO hydrogenation reactions, oxygen vacancies can still bind CO molecules, and H2 spilled-over from copper also competed for adsorption on such sites. Our spectroscopic observations demonstrate the existence of bifunctional active sites in which the metal sites catalyze CO2 dissociation whereas oxygen vacancies bind and activate CO molecules.

Surface Basicity of Metal@TiO2 to Enhance Photocatalytic Efficiency for CO2 Reduction.

Photocatalytic reduction of CO2 to valuable chemical fuels is of broad interest, given its potential to activate stable greenhouse CO2 using renewable energy input. We report how to choose the right metal cocatalysts in combination with the surface basicity of TiO2 to enhance their photocatalytic efficiency for CO2 photoreduction. Uniform ligand-free metal nanoparticles (NPs) of Ag, Cu, Au, Pd, and Pt, supported on TiO2, are active for CO2 photoreduction using water as an electron donor. The group XI metals show a high selectivity to CO and Ag/TiO2 is most active to produce CO at a rate of 5.2 µmol g-1 h-1. The group X metals, e.g., Pd and Pt, mainly generate hydrocarbons including methane and ethane, and Pd/TiO2 is slightly more active in methane production at a rate of 2.4 µmol g-1 h-1. The activity of these photocatalysts can be enhanced by varying the surface basicity of TiO2 with primary amines. However, proton reduction selectivity is greatly enhanced in the presence of amine except amine-modified Ag/TiO2, which shows an activity enhancement by 2.4 times solely for CO2 photoreduction as compared to that without amines without switching its selectivity to proton reduction. Using in situ infrared spectroscopy and CO stripping voltammetry, we demonstrate that the improvement of electron density and the low proton affinity of metal cocatalysts are of key importance in CO2 photoreduction. As a systematic study, our results provide a guideline on the right choice of metals in combination of the surface functionality to tune the photocatalytic efficiency of supported metal NPs on TiO2 for selective CO2 photoreduction.

FT-IR and 1H NMR studies of the state of solubilized water in water-in-oil microemulsions stabilized by mixtures of single- and double-tailed cationic surfactants.

The structure of solubilized water in water-in-n-heptane aggregates stabilized by mixtures of single- and double-tail quaternary ammonium surfactants, namely didodecyldimethylammonium chloride/dodecyltrimethylammonium chloride (DDAC/DTAC) or didodecyldimethylammonium bromide/dodecyltrimethylammonium bromide (DDAB/DTAB) was studied by two noninvasive techniques, (1)H NMR and FT-IR. In the former, the chemical shift data, δ(obs), were used to calculate the so-called deuterium/protium fractionation factor, φ(M), of the aggregate-solubilized water and were found to be unity. In the FT-IR study, upon increasing water/surfactant molar ratio, W, the frequency, ν(OD), of the HOD species decreases, while its full width at half height and its area increase. The results obtained from both techniques indicate that the water appears to be present as a single nano-phase and the structure varies continuously as a result of increasing W. In addition, the effect of changing the counter-ion (Br(-) or Cl(-)) on (1)H NMR and FT-IR results was investigated. In spite of the known difference in the dissociation of these counter-ions from micellar aggregates, this was found not to affect the state of solubilized water. This report gives further insight into the contradictory scientific debates on the structure of water in the polar nano-cores of microemulsions.