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.

A series of hybrid niobates HCa 2 Nb 3 O 10 ×RNH 2 , containing n-alkylamines (R = Me, Et, Pr, Bu, Hx, Oc) intercalated into the interlayer space, has been thoroughly studied concerning the photocatalytic hydrogen production from a model aqueous solution of methanol for the first time. All the hybrid photocatalysts were synthesized by the conventional ceramic technique followed by protonation and intercalation of nalkylamines. The products were characterized using XRD, Raman, IR and diffuse reflectance spectroscopy, TGA, CHN-analysis and SEM. Photocatalytic measurements were conducted according to an advanced scheme taking into account possible changes in the photocatalyst concentration because of sedimentation, pH shifts and exfoliation of the samples into nanoplatelets. Special attention was also paid to the feasible improvement of the photocatalytic activity of the samples via their modification with Pt nanoparticles as a cocatalyst. In the series of amine derivatives, the highest rate of hydrogen generation was demonstrated by the Pt-loaded HCa 2 Nb 3 O 10 ×BuNH 2 reaching apparent quantum efficiency of 13% in the 220-340 nm range. The initial HCa 2 Nb 3 O 10 showed comparable efficiency of 8.3% that is greater than for other amine derivatives. It was demonstrated that for the investigated samples the photocatalytic activity correlates with their ability of water intercalation.

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Nowadays, the efficient conversion of plant biomass components (alcohols, carbohydrates, etc.) into more energy-intensive fuels, such as hydrogen, is one of the urgent scientific and technological problems. The present study is the first one focused on the photoinduced hydrogen evolution from aqueous D-glucose and D-xylose using layered perovskite-like oxides HCa2Nb3O10, H2La2Ti3O10, and their organically modified derivatives that have previously proven themselves as highly active photocatalysts. The photocatalytic performance was investigated for the bare compounds and products of their surface modification with a 1 mass. % Pt cocatalyst. The photocatalytic experiments followed an innovative scheme including dark stages as well as the control of the reaction suspension’s pH and composition. The study has revealed that the inorganic−organic derivatives of the layered perovskite-like oxides can provide efficient conversion of carbohydrates into hydrogen fuel, being up to 8.3 times more active than the unmodified materials and reaching apparent quantum efficiency of 8.8%. Based on new and previously obtained data, it was shown that the oxides’ interlayer space functions as an additional reaction zone in the photocatalytic hydrogen production and the contribution of this zone to the overall activity is dependent on the steric characteristics of the sacrificial agent used.

The stability of platinized n-butylamine-intercalated layered titanate H2La2Ti3O10 during the process of photocatalytic hydrogen production from aqueous methanol under UV irradiation has been thoroughly investigated by means of XRD, CHN, TG, 13C NMR, BET, SEM and GC-MS analysis. It was revealed that n‑butylamine completely abandons the interlayer space and transforms into n‑butyraldehyde within 3 h of the reaction, while the particle morphology and specific surface area of the photocatalyst are preserved. The resulting solid phase contains carbon in at least two different oxidation states, which are attributed to the intermediate products of methanol oxidation bound to the perovskite matrix. The activity of the photocatalyst formed in this way is stable in time and strongly depends on the medium pH, which is not typical of either the parent H2La2Ti3O10 or TiO2. An approximate linear equation φ ≈ 29−2∙pH holds for the apparent quantum efficiency of hydrogen production in the 220–340 nm range at 1 mol. % methanol concentration. In the acidic medium, the photocatalyst under study outperforms the platinized H2La2Ti3O10 by more than one order of magnitude. The variation in methanol concentration allowed a maximum quantum efficiency of hydrogen production of 44% at 10 mol. % to be reached.