Nanoparticulate Perovskites for Photocatalytic Water Reduction.

SrTiO3 and BaTiO3 nanoparticles (NPs) were activated using H2O2 or aqueous HNO3, and pristine and activated NPs were functionalized with a 2,2'-bipyridine phosphonic acid anchoring ligand (1), followed by reaction with RuCl3.3H2O and bpy, RhCl3.3H2O and bpy, or RuCl3.3H2O. The surface-bound metal complex functionalized NPs were used for the photogeneration of H2 from water, and their activity was compared to related systems using TiO2 NPs. The role of pH during surface complexation was found to be important. The NPs were characterized using Fourier transform infrared (FTIR) and solid-state absorption spectroscopies, thermogravimetric analysis mass spectrometry (TGA-MS), and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), and the dihydrogen generation was analyzed using gas chromatography-mass spectrometry (GC-MS). Our findings indicate that extensively functionalized SrTiO3 or BaTiO3 NPs may perform better than TiO2 NPs for water reduction.

Attraction in Action: Reduction of Water to Dihydrogen Using Surface-Functionalized TiO2 Nanoparticles.

The reactivity of a heterogeneous rhodium(III) and ruthenium(II) complex-functionalized TiO2 nanoparticle (NP) system is reported. The ruthenium and rhodium metal complexes work in tandem on the TiO2 NPs surface to generate H2 through water reduction under simulated and normal sunlight irradiation. The functionalized TiO2 NPs outperformed previously reported homogeneous systems in turnover number (TON) and frequency (TOF). The influence of individual components within the system, such as pH, additive, and catalyst, were tested. The NP material was characterized using TGA-MS, 1H NMR spectroscopy, FTIR spectroscopy, solid absorption spectroscopy, and ICP-MS. Gas chromatography was used to determine the reaction kinetics and recyclability of the NP-supported photocatalyst.

Turning over on sticky balls: preparation and catalytic studies of surface-functionalized TiO2 nanoparticles.

We have investigated the reactivity of rhodium(iii) complex-functionalized TiO2 nanoparticles and demonstrate a proof-of-principle study of their catalytic activity in an alcohol oxidation carried out under aqueous conditions water in air. TiO2 nanoparticles (NPs) have been treated with (4-([2,2':6',2''-terpyridin]-4'-yl)phenyl)phosphonic acid, 1, to give the functionalized NPs (1)@TiO2. Reaction between (1)@TiO2 NPs and either RhCl3·3H2O or [Rh2(µ-OAc)4(H2O)2] produced the rhodium(iii) complex-functionalized NPs Rh(1)2@TiO2. The functionalized NPs were characterized using thermogravimetric analysis (TGA), matrix-assisted laser desorption ionization (MALDI) mass spectrometry, 1H NMR and FT-IR spectroscopies; the single crystal structures of [Rh(1)2][NO3]3·1.25[H3O][NO3]·2.75H2O and of a phosphonate ester derivative were determined. 1H NMR spectroscopy was used to follow the reaction kinetics and to assess the recyclability of the NP-supported catalyst. The catalytic activity of the Rh(1)2@TiO2 NPs was compared to that of a homogeneous system containing [Rh(1)2]3+, confirming that no catalytic activity was lost upon surface-binding. Rh(1)2@TiO2 NPs were able to withstand reaction temperatures of up to 100 °C for 24 days without degradation.

The SALSAC approach: comparing the reactivity of solvent-dispersed nanoparticles with nanoparticulate surfaces.

We demonstrate that the 'surface-as-ligand, surface-as-complex' (SALSAC) approach that we have established for annealed nanoparticulate TiO2 surfaces can be successfully applied to nanoparticles (NPs) dispersed in solution. Commercial TiO2 NPs have been activated by initial treatment with aqueous HNO3 followed by dispersion in water and heating under microwave conditions. We have functionalized the activated NPs with anchoring ligands 1-4; 1-3 contain one or two phosphonic acid anchoring groups and 4 has two carboxylic acid anchors; ligands 1, 2 and 4 contain 6,6'-dimethyl-2,2'-bipyridine (Me2bpy) metal binding domains and 3 contains a 2,2':6',2''-terpyridine (tpy) unit. Ligand functionalization of the activated NPs has been validated using infrared and 1H NMR spectroscopies, and thermogravimetric analysis. NPs functionalized with 1, 2 and 4 react with [Cu(MeCN)4][PF6] and those with 3 react with FeCl2·4H2O; metal binding has been investigated using solid-state absorption spectroscopy and scanning electron microscopy (SEM). Competitive binding of ligands 1-4 to TiO2 NPs has been investigated and shows preferential binding of phosphonic acid over carboxylic acid anchors. For the phosphonic acids, the binding orders are 3 > 1 > 2 which is rationalized in terms of relative pK a values (phosphonic acid and [HMe2bpy]+ or [Htpy]+) and the number of anchoring groups in the ligands. Ligand exchange between ligand-functionalized NPs and homoleptic metal complexes gives NPs functionalized with heteroleptic copper(i) or iron(ii) complexes.

Directed Insertion of Light-Activated Proteorhodopsin into Asymmetric Polymersomes from an ABC Block Copolymer.

Nanoscopic artificial vesicles containing functional protein transporters are fundamental for synthetic biology. Energy-providing modules, such as proton pumps, are a basis for simple nanoreactors. We report on the first insertion of a functional transmembrane protein into asymmetric polymersomes from an ABC triblock copolymer. The polymer with the composition poly(ethylene glycol)-poly(diisopropylaminoethyl methacrylate)-poly(styrenesulfonate) (PEG-PDPA-PSS) was synthesized by sequential controlled radical polymerization. PEG and PSS are two distinctively different hydrophilic blocks, allowing for a specific orientation of our protein, the light-activated proton pump proteorhodopsin (PR), into the final proteopolymersome. A very interesting aspect of the PEG-PDPA-PSS triblock copolymers is that it allowed for simultaneous vesicle formation and oriented insertion of PR simply by adjusting the pH. The intrinsic positive charge of PR's intracellular surface was enhanced by a His-tag, which aligns readily with the negative charges of the PSS on the outside of the polymersomes. The directed insertion of PR was confirmed by a light-dependent pH change of the proteopolymersome solution, indicating the intended orientation. We have hereby demonstrated the first successful oriented insertion of a proton pump into an artificial asymmetric membrane.