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.

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.

No abstract

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...

The brain activity is a very complex process, which is mainly characterized by the electroencephalogram (EEG). Moreover, there exist many interactions between the brain and other human body systems such as the cardiovascular system. Therefore, to explore these interactions a model was identified based on intelligent modeling tools (fuzzy-ARX). Signals generated from a previous work related to the modeling of the cardiovascular system were used as an input for the proposed model. EEG signals were measured for six male subjects and were used as an output for the proposed model. The model output was validated in both time and frequency domains for each subject. Furthermore, the validation results revealed that there exist good match between the measured EEG signals and the corresponding estimated EEG signals generated from the proposed model for each subject. Moreover, the model could be used as a descriptor for the relationships existed between the brain and the cardiovascular system afferents.