Search

The layered double hydroxides (LDHs) of transition metals are of great interest as building blocks for the creation of composite photocatalytic materials for hydrogen production, environmental remediation and other applications. However, the synthesis of most LDHs is reported only by the conventional coprecipitation method, which makes it difficult to control the catalyst's crystallinity. In the present study, ZnCr- and NiCr-LDHs have been successfully prepared using a facile hydrothermal approach. Varying the hydrothermal synthesis conditions allowed us to obtain target products with a controllable crystallite size in the range of 2–26 nm and a specific surface area of 45–83 m2∙g−1. The LDHs synthesized were investigated as photocatalysts of hydrogen generation from aqueous methanol. It was revealed that the photocatalytic activity of ZnCr-LDH samples grows monotonically with the increase in their average crystallite size, while that of NiCr-LDH ones reaches a maximum with intermediate-sized crystallites and then decreases due to the specific surface area reduction. The concentration dependence of the hydrogen evolution activity is generally consistent with the standard Langmuir–Hinshelwood model for heterogeneous catalysis. At a methanol content of 50 mol. %, the rate of hydrogen generation over ZnCr- and NiCr-LDHs reaches 88 and 41 μmol∙h−1∙g−1, respectively. The hydrothermally synthesized LDHs with enhanced crystallinity may be of interest for further fabrication of their nanosheets being promising components of new composite photocatalysts. [ABSTRACT FROM AUTHOR]

Nanosheets of layered perovskite-like oxides attract researchers as building blocks for the creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phases are difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliation procedure in aqueous solutions of bulky organic bases. The present study has considered systematically a relatively novel and efficient approach to a high-yield preparation of concentrated suspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths, exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged to separate the nanosheet-containing supernatant. The experiments included variations of a wide range of conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensions up to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the length of intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modified with short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation as compared to those with long-chain ones. It was also shown that the exfoliation efficiency depends more on the sample stirring time in the TBAOH solution than on the sonication duration. Analysis of the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic force microscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliation strategy appears to be convenient for the high-yield production of perovskite nanosheet-based materials for photocatalytic hydrogen production, environmental remediation and other applications. [ABSTRACT FROM AUTHOR]

A protonated and hydrated Dion-Jacobson-phase HSr2Nb3O10∙yH2O was used to prepare two series of inorganic–organic derivatives containing non-covalently intercalated n-alkylamines and covalently grafted n-alkoxy groups of different lengths, as they are promising hybrid materials for photocatalytic applications. Preparation of the derivatives was carried out both under the conditions of standard laboratory synthesis and by solvothermal methods. For all the hybrid compounds synthesized structure, quantitative composition, a type of bonding between inorganic and organic parts as well as light absorption range were discussed using powder XRD, Raman, IR and NMR spectroscopy, TG, elemental CHN analysis, and DRS. It was shown that the inorganic–organic samples obtained contain approximately one interlayer organic molecule or group per proton of the initial niobate, as well as some amount of intercalated water. In addition, the thermal stability of the hybrid compounds strongly depends on the nature of the organic component anchoring to the niobate matrix. Although non-covalent amine derivatives are stable only at low temperatures, covalent alkoxy ones can withstand heat up to 250 °C without perceptible decomposition. The fundamental absorption edge of both the initial niobate and the products of its organic modification lies in the near-ultraviolet region (370–385 nm). [ABSTRACT FROM AUTHOR]

Two series of hybrid inorganic–organic materials, prepared via interlayer organic modification of protonated Ruddlesden–Popper phases HLnTiO4 (Ln = La, Nd) with n-alkylamines and n-alkoxy groups of various lengths, have been systematically studied with respect to photocatalytic hydrogen evolution from aqueous methanol under near-ultraviolet irradiation for the first time. Photocatalytic measurements were organized in such a way as to control a wide range of parameters, including the hydrogen generation rate, quantum efficiency of the reaction, potential dark activity of the sample, its actual volume concentration in the suspension, pH of the medium and stability of the photocatalytic material under the operating conditions. The insertion of the organic modifiers into the interlayer space of the titanates allowed obtaining new, more efficient photocatalytic materials, being up to 68 and 29 times superior in the activity in comparison with the initial unmodified compounds HLnTiO4 and a reference photocatalyst TiO2 P25 Degussa, respectively. The hydrogen evolution rate over the samples correlates with the extent of their interlayer hydration, as in the case of the inorganic–organic derivatives of other layered perovskites reported earlier. However, the HLnTiO4-based samples demonstrate increased stability with regard to the photodegradation of the interlayer organic components as compared with related H2Ln2Ti3O10-based hybrid materials. [ABSTRACT FROM AUTHOR]

Photocatalytic activity of HB2Nb3O10 perovskite nanosheets (B = Ca, Sr) has been systematically investigated in the reactions of hydrogen production, depending on the method of the photocatalyst preparation: using the pristine nanosheets in the parent suspension without reassembly, filtered nanosheets as well as nanosheets restacked by hydrochloric acid. Photocatalytic measurements were organized in such a way as to control a wide range of parameters, including the hydrogen generation rate, quantum efficiency of the reaction, potential dark activity of the sample as well as stability and pH of the reaction suspension. Exfoliation of the niobates into nanosheets allowed obtaining efficient photocatalysts surpassing the initial bulk materials in the activity up to 55 times and providing apparent quantum efficiency up to 20.8% after surface decoration with a Pt cocatalyst. Among the reassembled samples, greater hydrogen evolution activity was exhibited by simply filtered nanosheets that, unlike the HCl-restacked ones, were found to possess much lower specific surface area in a dry state but contain a perceptible amount of tetrabutylammonium cations on the surface. The activity difference, potentially, is associated with the fact that the filtered nanosheets undergo ultrasonic disaggregation before photocatalytic tests much easier than their HCl-restacked counterparts and, thanks to this, have greater active surface in the reaction suspension. In addition, the enhanced activity of the filtered nanosheets may be due to the presence of tetrabutylammonium as an organic modifier on their surface, which is consistent with the high photocatalytic performance of organically modified layered perovskites considered in our previous reports. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Structures of partially and completely protonated Ruddlesden-Popper phases, H0.7Na0.3NdTiO4·0.3H2O and HNdTiO4, have been established by means of neutron and X-ray diffraction analysis and compared among themselves as well as with that of the initial titanate NaNdTiO4. It was shown that while interlayer sodium cations in the partially protonated form are coordinated by nine oxygen atoms, including one related to intercalated water, in the fully protonated compound the ninth oxygen proves to be an axial anion belonging to the opposite slab of titanium-oxygen octahedra. Moreover, the partially protonated titanate was found to significantly differ from the other two in the octahedron distortion pattern. It is characterized by a weakly pronounced elongation of the octahedra towards the Nd-containing interlayer space making Ti4+ cations practically equidistant from both axial oxygen atoms, which is accompanied by a low-frequency shift of the bands relating to the asymmetric stretching mode of axial Ti-O bonds observed in the Raman spectra. [ABSTRACT FROM AUTHOR]

Abstract: The K2La2Ti3O10 layered oxide was synthesized by high-temperature technique. Ion exchange properties of K2La2Ti3O10·H2O were investigated by continuous potentiometric titration of its suspension in KOH with HCl. The shape of the titration curve indicates that the ion-exchange reaction of interlayer K+ to H+ proceeds at pH 7.5–8.5 at the rate as high as 5% min−1. Samples obtained during the titration experiment at pH 9.8, 4.8, and 1.4 were examined by XRD, TG, ICP-AES, and SEM–EDX. Protonation already occurs at pH > 9.8, while at pH 4.8 a substitution degree of 76% is observed. K2La2Ti3O10 was found to be unstable against K+ leaching, which results in irreversible ion-exchange even when the sample is washed with distilled water. The protonation of the layered oxide significantly suppresses its photocatalytic activity in the reaction of hydrogen production from aqueous isopropanol solution, which correlates with the decreasing amount of intercalated water.Graphical abstract: [ABSTRACT FROM AUTHOR]

The Rb2La2Ti3O10 layered oxide was synthesized by the solid-state method. Three phases with different protonation degrees and intercalated water contents were obtained from the initial compound by the treatment with distilled water and hydrochloric acid. The obtained samples were characterized by powder X-ray diffraction, SEM, X-ray microanalysis, BET, DRS, and TG. It was found that the complete ion exchange of Rb+ for H+ in the layered oxide Rb2La2Ti3O10 proceeds through the formation of two metastable intermediate phases with average protonation degrees of 0.5 and 0.75, which successively transform from one to another. Each of these phase transformations is accompanied not only by the contraction of the interlayer distance but also by the displacement of adjacent perovskite layers by 1/2 of the cell parameter which results in the change in the space group. The photocatalytic activity of obtained samples decreases with the increase in the protonation degree, which correlates with the decrease in the intercalated water content. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The photocatalytic activity of layered perovskite-like oxides in water splitting reaction is dependent on the hydration level and species located in the interlayer slab: simple or complex cations as well as hydrogen-bonded or non-hydrogen-bonded H2O. To study proton localization and dynamics in the HCa2Nb3O10·yH2O photocatalyst with different hydration levels (hydrated—α-form, dehydrated—γ-form, and intermediate—β-form), complementary Nuclear Magnetic Resonance (NMR) techniques were applied. 1H Magic Angle Spinning NMR evidences the presence of different proton containing species in the interlayer slab depending on the hydration level. For α-form, HCa2Nb3O10·1.6H2O, 1H MAS NMR spectra reveal H3O+. Its molecular motion parameters were determined from 1H spin-lattice relaxation time in the rotating frame (T1ρ) using the Kohlrausch-Williams-Watts (KWW) correlation function with stretching exponent β = 0.28: E a = 0.210 2 eV, τ 0 = 9.0 1   ×   10 − 12 s. For the β-form, HCa2Nb3O10·0.8H2O, the only 1H NMR line is the result of an exchange between lattice and non-hydrogen-bonded water protons. T1ρ(1/T) indicates the presence of two characteristic points (224 and 176 K), at which proton dynamics change. The γ-form, HCa2Nb3O10·0.1H2O, contains bulk water and interlayer H+ in regular sites. 1H NMR spectra suggest two inequivalent cation positions. The parameters of the proton motion, found within the KWW model, are as follows: E a = 0.217 8 eV, τ 0 = 8.2 9   ×   10 − 10 s. [ABSTRACT FROM AUTHOR]

In the present work, we report the results on exfoliation and coating formation of inorganic–organic hybrids based on the layered perovskite-like bismuth titanate H2K0.5Bi2.5Ti4O13·H2O that could be prepared by a simple ion exchange reaction from a Ruddlesden–Popper phase K2.5Bi2.5Ti4O13. The inorganic–organic hybrids were synthesized by intercalation reactions. Exfoliation into nanosheets was performed for the starting hydrated protonated titanate and for the derivatives intercalated by n-alkylamines to study the influence of preliminary intercalation on exfoliation efficiency. The selected precursors were exfoliated in aqueous solutions of tetrabutylammonium hydroxide using facile stirring and ultrasonication. The suspensions of nanosheets obtained were characterized using UV–vis spectrophotometry, dynamic light scattering, inductively coupled plasma spectroscopy, and gravimetry. Nanosheets were coated on preliminarily polyethyleneimine-covered Si substrates using a self-assembly procedure and studied using atomic force and scanning electron microscopy. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 n -alkylamines. 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., (Copyright © 2020 Voytovich, Kurnosenko, Silyukov, Rodionov, Minich and Zvereva.)

New organic-inorganic hybrids have been synthesized by the intercalation of n -alkylamines (methylamine, ethylamine, n -propylamine, n -butylamine, n -hexylamine, and n -octylamine) into the structure of the protonated and hydrated form of the perovskite-like layered titanate H 2 K 0.5 Bi 2.5 Ti 4 O 13 ·H 2 O (HKBT 4 ·H 2 O). The possibility of the synthesis of the hybrid materials was studied in a wide range of conditions. It was found that interlayer water plays a crucial role in the formation of intercalated hybrids. The obtained compounds were characterized with powder X-ray diffraction analysis; Raman, IR, and NMR spectroscopies; thermogravimetry (TG), TG coupled with mass spectrometry, and CHN analyses; and scanning electron microscopy. It was suggested that the intercalated n -alkylamines exist in the form of alkylammonium ions forming a paraffin-like bilayer with an average tilting angle of ∼77.5°. The obtained HKBT 4 ×RNH 2 compounds contain 0.4-0.7 n -alkylamine molecules per formula unit as well as the varied amount of intercalated water. By gentle heating, they can be obtained as dehydrated forms, which are thermally stable up to 250 °C., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

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., (Copyright © 2019 Rodionov, Maksimova, Pozhidaev, Kurnosenko, Silyukov and Zvereva.)