No abstract

Blends of fly ash and natural calcite, mechanically activated for 0–400 s in a planetary mill, were used to synthesize geopolymers at ambient temperature. The calcite content in the blends was 0–10 wt.%. Sodium hydroxide solution was used as an alkaline agent. Mechanical activation of the raw material considerably enhanced its reactivity with respect to the alkaline agent, as was observed using Fourier-transform infrared spectroscopy, isothermal conduction calorimetry, thermogravimetry coupled with mass spectrometry analysis of the evolved gas, and SEM/EDS. The addition of calcite to the fly ash improved the compressive strength of the geopolymers, especially during the early age of curing. For 7 d aged geopolymers based on the 90% fly ash + 10% calcite blend, the strength was 8.0-, 3.5- and 2.9-fold higher than that for the geopolymers based on the unblended fly ash for 30 s, 180 s and 400 s mechanical activation time, respectively. Using Mössbauer spectroscopy, it was revealed that iron present in the fly ash did not play a significant part in the geopolymerization process. The dominant reaction product was sodium containing aluminosilicate hydrogel (N-A-S-H gel). Calcite was found to transform, to a small extent, to vaterite and Ca(OH)2 in the course of the geopolymerization.

A layered perovskite-type oxide intercalated with n-butylamine is reported as an efficient photocatalyst for hydrogen production from aqueous solutions of alcohols for the first time. The hybrid photocatalyst H 2 Nd 2 Ti 3 O 10 ×BuNH 2 was synthesized by solid-state ceramic method followed by protonation, intercalation of methylamine and subsequent substitution by n-butylamine. The product was characterized by powder XRD, TGA, STA-MS, DRS, IR, and Raman spectroscopy, CHN analysis, SEM. Intercalation of n-butylamine caused a dramatic increase in photocatalytic activity of H 2 Nd 2 Ti 3 O 10 in the reaction of hydrogen evolution from aqueous solutions of methanol, ethanol, and n-butanol under UV radiation. While the non-intercalated Pt-loaded H 2 Nd 2 Ti 3 O 10 showed a maximum quantum efficiency of only 2% in the 220-340 nm range, the efficiency for hybrid samples reached 23% under the same conditions and after variation of experimental parameters even 52% efficiency was achieved. This effect may be associated with the significant expansion of the interlayer space, which is considered as a separate reaction zone.

Two series of hybrid inorganic-organic derivatives, obtained via the modification of protonated Ruddlesden–Popper phases H2Ln2Ti3O10 (Ln = La, Nd) with intercalated n-alkylamines and grafted n-alkoxy groups, have been systematically investigated in relation to photocatalytic hydrogen production from a model of 1 mol % aqueous solution of methanol for the first time. Photocatalytic measurements were performed both for bare samples and for their composites with Pt nanoparticles as a cocatalyst using an advanced scheme, including dark stages, monitoring of the volume concentration of the sample in the reaction suspension during the experiment, shifts of its pH and possible exfoliation of layered compounds into nanolayers. It was found that the incorporation of organic components into the interlayer space of the titanates increases their photocatalytic activity up to 117 times compared with that of the initial compounds. Additional platinization of the hybrid samples’ surface allowed for achieving apparent quantum efficiency of hydrogen evolution of more than 40%. It was established that the photocatalytic activity of the hybrid samples correlates with the hydration degree of their interlayer space, which is considered a separate reaction zone in photocatalysis, and that hydrogen indeed generates from the aqueous methanol solution rather than from organic components of the derivatives.

A series of hybrid inorganic–organic niobates HCa2Nb3O10×ROH, containing n-alkoxy groups of primary alcohols (R = Me, Et, Pr, Bu, Hx, and Dc) grafted in the interlayer space, has been studied for the first time in relation to photocatalytic hydrogen generation from a model 1 mol % aqueous solution of methanol under ultraviolet irradiation. Photocatalytic activity was measured both for bare samples and for their composites with Pt nanoparticles as a cocatalyst. The advanced measurement scheme allowed monitoring the volume concentration of a sample in a suspension during the experiment, its pH, and possible exfoliation of layered compounds into nanolayers. In the series of n-alkoxy derivatives, the maximum rate of hydrogen evolution was achieved over a Pt-loaded ethoxy derivative HCa2Nb3O10×EtOH/Pt. Its apparent quantum efficiency of 20.6% in the 220–350 nm range was found not to be caused by changes in the light absorption region or specific surface area upon ethanol grafting. Moreover, the amounts of hydrogen released during the measurements significantly exceeded those of interlayer organic components, indicating that hydrogen is generated from the reaction solution rather than from the hybrid material.