RESUMO
Recently, global-scale efforts have been conducted for the electroreduction of CO2 as a potentially beneficial pathway for the conversion of greenhouse gases to useful chemicals and renewable fuels. This study focuses on the development of selective and sustainable electrocatalysts for the reduction of aqueous CO2 to CO. A RuIIcomplex [Ru(tptz)(ACN)Cl2] (RCMP) (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine, ACN = acetonitrile) was prepared as a molecular electrocatalyst for the CO2 reduction reaction in an aqueous solution. Density functional theory-calculated frontier molecular orbitals suggested that the tptz ligand plays a key role in dictating the electrocatalytic reactions. The RCMP electrocatalyst was grafted onto the graphene oxide (GO) surface both noncovalently (GO/RCMP) and covalently (GO-RCMP). The field emission scanning electron microscopy and elemental distribution analyses revealed the homogeneous distribution of the complex onto the GO sheet. The photoluminescence spectra confirmed accelerated charge-transfer in both nanohybrids. Compared to the bare complex, the GO-RCMP and GO/RCMP nanohybrids showed enhanced electrocatalytic activity, achieving >95% and 90% Faradaic efficiencies for CO production at more positive onset potentials, respectively. The GO-RCMP nanohybrid demonstrated outstanding electrocatalytic activity with a current of â¼84 µA. The study offers a perspective on outer- and inner-sphere electron-transfer mechanisms for electrochemical energy conversion systems.
RESUMO
TiO2 is one of the most widely used semiconductors for photocatalytic reactions. However, its wide bandgap energy and fast charge recombination limit its catalytic activity. Thus, herein, a new Ru(ii) polypyridyl complex, [Ruii(tptz)(CH3CN)Cl2] (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine), was synthesized and used as a visible-light photosensitizer dye for improving the light harvesting and quantum efficiency of TiO2. Accordingly, a well-designed nanostructured photocatalyst was proposed using mesoporous TiO2 nanocrystals coupled with reduced graphene oxide (rGO) and the polypyridyl Ru(ii) complex, which was tested for the photocatalytic degradation of atrazine (ATZ) as a model of emerging water contaminants. Specifically, the Ru complex (Ru-CMP) served as an electron donor, while rGO acted as an electron acceptor, and the synergistic effect between them promoted the separation of electron-hole pairs and suppressed the charge recombination in the hybridized species. Structural analysis indicated that the TiO2 nanoparticles with an anatase crystal structure had a mesoporous texture and were homogeneously coated on the rGO sheets. The detailed FT-IR, Raman, XPS and UV-vis absorption spectroscopic analyses combined with EDS mapping clearly confirmed the successful loading of the Ru complex onto the catalyst. The PL and EIS results revealed that the addition of the Ru-CMP photosensitizer enhanced the charge separation and transport. The gas-phase geometry and energies of the molecular orbitals of the Ru complex were evaluated via DFT calculations. The results from the DFT calculations were consistent with the experimental results. Compared to pure TiO2, the as-synthesized Ru-CMP-TiO2/rGO hybrid exhibited significantly enhanced photocatalytic activity for the degradation of ATZ. The rate of ATZ degradation in the developed photocatalytic process with the Ru-CMP-TiO2/rGO hybrid was 9 times that with commercial TiO2. The enhanced photocatalytic activity of the prepared catalyst can be attributed to its better light harvesting and efficient electron transportation due to its more suitable LUMO position than the conduction band of TiO2. Moreover, the excellent conductivity and adsorption capacity of graphene contributed to the increase in photocatalytic activity. Thus, these features make the Ru-CMP-TiO2/rGO hybrid nanomaterial an excellent candidate for the photocatalytic purification of contaminated water.
