Conformal Coverage of ZnO Nanowire Arrays by ZnMnO3 : Room-temperature Photodeposition from Aqueous Solution.

Compositionally and structurally complex semiconductor oxide nanostructures gain importance in many energy-related applications. Simple and robust synthesis routes ideally complying with the principles of modern green chemistry are therefore urgently needed. Here we report on the one-step, room-temperature synthesis of a crystalline-amorphous biphasic ternary metal oxide at the ZnO surface using aqueous precursor solutions. More specifically, conformal and porous ZnMnO3 shells are photodeposited from KMnO4 solution onto immobilized ZnO nanowires acting not only as the substrate but also as the Zn precursor. This water-based, low temperature process yields ZnMnO3 /ZnO composite electrodes featuring in 1 M Na2 SO4 aqueous solution capacitance values of 80-160 F g-1 (as referred to the total mass of the porous film i. e. the electroactive ZnMnO3 phase and the ZnO nanowire array). Our results highlight the suitability of photodeposition as a simple and green route towards complex functional materials.

Substrate-Enabled Room-Temperature Electrochemical Deposition of Crystalline ZnMnO3.

Mixed transition metal oxides have emerged as promising electrode materials for electrochemical energy storage and conversion. To optimize the functional electrode properties, synthesis approaches allowing for a systematic tailoring of the materials' composition, crystal structure and morphology are urgently needed. Here we report on the room-temperature electrodeposition of a ternary oxide based on earth-abundant metals, specifically, the defective cubic spinel ZnMnO3 . In this unprecedented approach, ZnO surfaces act as (i) electron source for the interfacial reduction of MnO4 - in aqueous solution, (ii) as substrate for epitaxial growth of the deposit and (iii) as Zn precursor for the formation of ZnMnO3 . Epitaxial growth of ZnMnO3 on the lateral facets of ZnO nanowires assures effective electronic communication between the electroactive material and the conducting scaffold and gives rise to a pronounced 2-dimensional morphology of the electrodeposit forming - after partial delamination from the substrate - twisted nanosheets. The synthesis strategy shows promise for the direct growth of different mixed transition metal oxides as electroactive phase onto conductive substrates and thus for the fabrication of binder-free nanocomposite electrodes.

Impact of Nanoparticle Consolidation on Charge Separation Efficiency in Anatase TiO2 Films.

Mesoporous films and electrodes were prepared from aqueous slurries of isolated anatase TiO2 nanoparticles. The resulting layers were annealed in air at temperatures 100°C ≤ T ≤ 450°C upon preservation of internal surface area, crystallite size and particle size. The impact of processing temperature on charge separation efficiency in nanoparticle electrodes was tracked via photocurrent measurements in the presence of methanol as a hole acceptor. Thermal annealing leads to an increase of the saturated photocurrent and thus of the charge separation efficiency at positive potentials. Furthermore, a shift of capacitive peaks in the cyclic voltammograms of the nanoparticle electrodes points to the modification of the energy of deep traps. Population of these traps triggers recombination possibly due to the action of local electrostatic fields attracting photogenerated holes. Consequently, photocurrents saturate at potentials, at which deep traps are mostly depopulated. Charge separation efficiency was furthermore investigated for nanoparticle films and was tracked via the decomposition of hydrogen peroxide. Our observations evidence an increase of charge separation efficiency upon thermal annealing. The effect of particle consolidation, which we associate with minute atomic rearrangements at particle/particle contacts, is attributed to the energetic modification of deep traps and corresponding modifications of charge transport and recombination, respectively.

Photoelectrochemical Properties of SnO2 Photoanodes Sensitized by Cationic Perylene-Di-Imide Aggregates for Aqueous HBr Splitting.

Perylene-sensitized mesoporous SnO2 films were used as electrodes for photoelectrochemical HBr splitting in aqueous solution. Upon AM 1.5 G illumination a 3-4 fold increase of the saturated photocurrent was observed when decreasing the pH of the aqueous solution from pH 3 to pH 0 (j max = 0.05 ± 0.01 mAcm-2 at pH 3 and 0.17 ± 0.02 mAcm-2 at pH 0, respectively). A detailed spectroscopic and electrochemical analysis of the hybrid material was carried out in order to address the impact of interfacial energetics on charge separation dynamics. UV/Vis spectroelectrochemical measurements showed that the energy of semiconductor states in such systems can be adjusted independently from the molecular levels by varying proton concentration. Photoelectrochemical measurements and ns-µs transient absorption spectroscopy reveal that pH-related changes of the interfacial energetics have only a minor impact on the charge injection rate. An increase of the proton concentration improves charge collection mainly by retarding recombination, which in the case of Br- oxidation is in critical competition with perylene regeneration. Control of the back recombination appears to be a key feature in heterogeneous molecular systems tasked to drive energetically demanding redox reactions.

Particle Consolidation and Electron Transport in Anatase TiO2 Nanocrystal Films.

A sequence of chemical vapor synthesis and thermal annealing in defined gas atmospheres was used to prepare phase-pure anatase TiO2 nanocrystal powders featuring clean surfaces and a narrow particle size distribution with a median particle diameter of 14.5 ± 0.5 nm. Random networks of these nanocrystals were immobilized from aqueous dispersions onto conducting substrates and are introduced as model systems for electronic conductivity studies. Thermal annealing of the immobilized films at 100 °C < T < 450 °C in air was performed to generate particle-particle contacts upon virtual preservation of the structural properties of the nanoparticle films. The distribution of electrochemically active electronic states as well as the dependence of the electronic conductivity on the Fermi level position in the semiconductor films was studied in aqueous electrolytes in situ using electrochemical methods. An exponential distribution of surface states is observed to remain unchanged upon sintering. However, capacitive peaks corresponding to deep electron traps in the nanoparticle films shift positive on the potential scale evidencing an increase of the trapping energy upon progressive thermal annealing. These peaks are attributed to trap states at particle-particle interfaces in the random nanocrystal network (i.e., at grain boundaries). In the potential region, where the capacitive peaks are detected, we observe an exponential conductivity variation by up to 5 orders of magnitude. The potential range featuring the exponential conductivity variation shifts positive by up to 0.15 V when increasing the sintering temperature from 100 to 450 °C. Importantly, all films approach a potential- and sintering-temperature-independent maximum conductivity of ∼10-4 Ω-1·cm-1 at more negative potentials. On the basis of these results we introduce a qualitative model, which highlights the detrimental impact of electron traps located on particle-particle interfaces on the electronic conductivity in random semiconductor nanoparticle networks.